Decomposing polymer binders for additive manufacturing feedstock

ABSTRACT

Techniques and compositions are disclosed for feedstocks with powder/binder systems for three-dimensional printing, such as fused filament fabrication. For example, a feedstock may include a primary binder and a secondary binder for supporting a shape of a three-dimensional object through processing into a final part. The primary binder may include a high molecular weight polymer useful to achieve high print quality and strength of the three-dimensional object in initial processing. Further, the high molecular weight polymer may be chemically decomposed, and thus rapidly debound from the three-dimensional object, through exposure to a solvent. The secondary binder may be substantially insoluble in the solvent such that the secondary binder may remain to support a net shape of the three-dimensional object in subsequent processing. Accordingly, the high molecular weight polymer in the primary binder, in combination with the second binder, may be useful for rapid three-dimensional manufacturing of high quality parts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Prov. Pat. App. No. 62/434,014,filed on Dec. 14, 2016, U.S. Prov. Pat. App. No. 62/489,271, filed onApr. 24, 2017, and U.S. Prov. Pat. App. No. 62/491,170, filed Apr. 27,2017, with the entire contents of each of these applications herebyincorporated herein by reference.

This application is also related to International Pat. App. No.PCT/US17/66526, filed on Dec. 14, 2017, with the entire contents herebyincorporated herein by reference.

FIELD

The systems and methods described herein relate to additivemanufacturing, and more specifically to additive manufacturing withpowder/binder systems suitable for use with fused filament fabricationand other techniques.

BACKGROUND

Certain additive manufacturing techniques include extrusion of feedstockto form a three-dimensional object. Material requirements associatedwith handling feedstock for extrusion, however, may differ from or maybe at least partially incompatible with material requirements forappropriate formation of the material of the feedstock into ahigh-quality part. Such differences in material requirements canparticularly impact the usefulness of extrusion-based additivemanufacturing techniques in forming metal objects. Thus, there remains aneed for materials suitable for fabricating metal net shape objectsusing extrusion-based additive manufacturing techniques.

SUMMARY

Techniques and compositions are disclosed for three-dimensional printingwith powder/binder systems including but not limited to metal injectionmolding powder materials, highly-filled polymer composites, and anyother materials suitable for handling with various additivemanufacturing techniques, and further suitable for subsequent debindingand thermal processing into a final object.

Techniques and compositions are disclosed for feedstocks withpowder/binder systems for three-dimensional printing, such as fusedfilament fabrication. For example, a feedstock may include a primarybinder and a secondary binder for supporting a shape of athree-dimensional object through processing into a final part. Theprimary binder may include a high molecular weight polymer useful toachieve high print quality and strength of the three-dimensional objectin initial processing. Further, the high molecular weight polymer may bechemically decomposed, and thus rapidly debound from thethree-dimensional object, through exposure to a solvent. The secondarybinder may be substantially insoluble in the solvent such that thesecondary binder may remain to support a net shape of thethree-dimensional object in subsequent processing. Accordingly, the highmolecular weight polymer in the primary binder, in combination with thesecond binder, may be useful for rapid three-dimensional manufacturingof high quality parts.

In one aspect, a method of additive manufacturing disclosed hereinincludes moving one or more nozzles along an extrusion path relative toa build plate, extruding a feedstock through the one or more nozzles,the feedstock including a binder system and a powder material dispersedin the binder system, the extrusion of the feedstock forming athree-dimensional object along the extrusion path, exposing thethree-dimensional object to a chemical solution, the chemical solutionchemically decomposing a polymer of a primary binder of the bindersystem, and the chemical decomposition of the polymer occurs during achemical dissolution of at least a portion of the primary binder fromthe three-dimensional object as a secondary binder of the binder systemsupports a shape of the three-dimensional object, debinding thesecondary binder from the three-dimensional object, and densifying thepowder material in the three-dimensional object to form a final part.

The secondary binder may be substantially insoluble in the chemicalsolution to which the three-dimensional object is exposed. The polymerof the primary binder may be a high molecular weight polymer. The highmolecular weight polymer of the primary binder may have a molecularweight of greater than about 100,000 g/mol. The secondary binder mayinclude a second polymer, and the second polymer may have a molecularweight less than or about equal to a molecular weight of the highmolecular weight polymer. The powder material may include one or more ofa metal, a metal alloy, or a ceramic. The primary binder may furtherinclude a wax soluble in the chemical solution as the three-dimensionalobject is exposed to the chemical solution. The primary binder may bedebound from the three-dimensional object leaving a waste streamincluding aqueous monosaccharides. Densifying the powder may include oneor more of sintering the three-dimensional object or infiltrating thethree-dimensional object with a liquid metal.

In another aspect, a feedstock for additive manufacturing disclosedherein includes a powder material, a primary binder containing a highmolecular weight polymer chemically decomposable and dissoluble uponexposure to a chemical solution, and a secondary binder for retaining,during a thermal process, a shape of a part formed from the feedstock,the secondary binder substantially insoluble in the chemical solutionwith which the high molecular weight polymer is depolymerizable.

The high molecular weight polymer may have a molecular weight of greaterthan about 100,000 g/mol. The chemical solution may include a catalystto for the chemical decomposition of the high molecular weight polymer.The chemical decomposition may occur via depolymerization. The highmolecular weight polymer of the primary binder may include at least oneof a thermoplastic polysaccharide, polylactic acid, polyglycolic acid,poly(lactide)-co-(caprolactone), copolymers containing styrene blocks,polyethylene glycol, PEG-PMMA, a urethane ester, and a polyanhydride.The high molecular weight polymer may be chemically decomposable in oneor more of an aqueous solution or an alkaline solution. the chemicalsolution is an aqueous solution and the high molecular weight polymer ishydrolysable in the aqueous solution. The high molecular weight polymermay be chemically decomposable in an acidic solution.

In another aspect, a three-dimensional object disclosed herein includesa plurality of layers collectively forming the three-dimensional object,each layer coupled to at least one other layer, and each layer includinga powder material, a primary binder containing a high molecular weightpolymer chemically decomposable and dissoluble with a chemical solution,and a secondary binder for retaining, during a thermal process, a shapeof the three-dimensional object, the secondary binder substantiallyinsoluble in the chemical solution with which the high molecular weightpolymer is chemically decomposable.

The high molecular weight polymer may have a molecular with of greaterthan about 100,000 g/mol. The secondary binder may include a secondpolymer, and the second polymer may have a molecular weight less thanabout equal to a molecular weight of the high molecular weight polymer.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, features and advantages of the devices,systems, and methods described herein will be apparent from thefollowing description of particular embodiments thereof, as illustratedin the accompanying drawings. The drawings are not necessarily to scale,emphasis instead being placed upon illustrating the principles of thedevices, systems, and methods described herein.

FIG. 1 is a block diagram of an additive manufacturing system for usewith composites.

FIG. 2 is a flow chart of an exemplary method for printing withcomposites.

FIG. 3 is a schematic representation of an additive manufacturing systemfor use with metal injection molding materials.

FIG. 4 is a schematic representation of a stereolithography processusing a metallic powder and an ultraviolet-curable binder.

FIG. 5 is a schematic representation of a laser binding process forusing powder metallurgy materials.

FIG. 6 is a schematic representation of the use of finishing materialsin a fabricated object.

FIG. 7 is a perspective view of a number of drive wheels suitable fordriving a feedstock in a fused filament fabrication (FFF) process.

FIG. 8A is a side view of a feedstock for a fused filament fabrication(FFF) process.

FIG. 8B is a side cross-sectional view of the feedstock of FIG. 8A alongline A-A in FIG. 8A.

FIG. 8C is an end view of the feedstock of FIG. 8A.

FIG. 9 is a flow chart of an exemplary method of forming a compositefeedstock.

FIG. 10 is a flow chart of an exemplary method of additive manufacturingusing a spoolable feedstock.

FIG. 11 is a flow chart of an exemplary method of additive manufacturingwith a feedstock including a chemically decomposable high molecularweight polymer as a component of a primary binder of a binder system.

FIG. 12 is a flow chart of an exemplary method of additive manufacturingwith a feedstock including a dissolvable high molecular weight polymeras a component of a primary binder of a binder system.

FIG. 13 is a cross-sectional side view of a three-dimensional objectincluding a spatial gradient of a first primary binder of a first bindersystem relative to a second primary binder of a second binder system.

FIG. 14 is a flow chart of an exemplary method for additivemanufacturing of a three-dimensional object having a spatialdistribution of at least one component of a first binder system relativeto at least one component of a second binder system.

DESCRIPTION

Embodiments will now be described with reference to the accompanyingfigures. The foregoing may, however, be embodied in many different formsand should not be construed as limited to the illustrated embodimentsset forth herein.

All documents mentioned herein are hereby incorporated by reference intheir entirety. References to items in the singular should be understoodto include items in the plural, and vice versa, unless explicitly statedotherwise or clear from the text. Grammatical conjunctions are intendedto express any and all disjunctive and conjunctive combinations ofconjoined clauses, sentences, words, and the like, unless otherwisestated or clear from the context. Thus, unless otherwise specified ormade clear from the context, the term “or” should generally beunderstood to mean “and/or” and, similarly, the term “and” shouldgenerally be understood to mean “and/or.”

Recitation of ranges of values herein are not intended to be limiting,referring instead individually to any and all values falling within therange, unless otherwise indicated herein, and each separate value withinsuch a range is incorporated into the specification as if it wereindividually recited herein. The words “about,” “approximately” or thelike, when accompanying a numerical value, are to be construed asindicating a deviation as would be appreciated by one of ordinary skillin the art to operate satisfactorily for an intended purpose. Similarly,words of approximation such as “approximately” or “substantially” whenused in reference to physical characteristics, should be understood tocontemplate a range of deviations that would be appreciated by one ofordinary skill in the art to operate satisfactorily for a correspondinguse, function, purpose, or the like. Ranges of values and/or numericvalues are provided herein as examples only, and do not constitute alimitation on the scope of the described embodiments. Where ranges ofvalues are provided, they are also intended to include each value withinthe range as if set forth individually, unless expressly stated to thecontrary. The use of any and all examples, or exemplary language(“e.g.,” “such as,” or the like) provided herein, is intended merely tobetter illuminate the embodiments and does not pose a limitation on thescope of the embodiments. No language in the specification should beconstrued as indicating any unclaimed element as essential to thepractice of the embodiments.

In the following description, it is understood that terms such as“first,” “second,” “top,” “bottom,” “up,” “down,” and the like, arewords of convenience and are not to be construed as limiting terms.

FIG. 1 is a block diagram of an additive manufacturing system for usewith composites. The additive manufacturing system may include athree-dimensional printer 100 (or simply printer 100) that depositsmetal using fused filament fabrication. Fused filament fabrication iswell known in the art and, with suitable adaptations described ingreater detail below, may be usefully employed for additivemanufacturing to accommodate the forces, temperatures and otherenvironmental requirements typical of the metallic injection moldingmaterials contemplated herein. In general, the printer 100 may include afeedstock 102 propelled by a drive train 104 and heated to a workablestate by a liquefaction system 106, and then dispensed through one ormore nozzles 110. By concurrently controlling a robotic system 108 toposition the one or more nozzles 110 along an extrusion path, an object112 may be fabricated on a build plate 114 within a build chamber 116.In general, a control system 118 manages operation of the printer 100 tofabricate the object 112 according to a three-dimensional model using afused filament fabrication process or the like.

A variety of commercially available compositions have been engineeredfor metal injection molding (“MIM”). These highly engineered materialscan also be adapted for use as a feedstock 102 in printing techniquessuch as fused filament fabrication. For example, MIM feedstockmaterials, when suitably shaped, may be usefully extruded throughnozzles typical of commercially available FFF machines, and aregenerally flowable or extrudable within typical operating temperatures(e.g., 160-250 degrees Celsius) of such machines. This temperature rangemay depend on the binder—e.g., some binders achieve appropriateviscosities at about 205 degrees Celsius, while others achieveappropriate viscosities at lower temperatures such as about 160-180 Cdegrees Celsius. One of ordinary skill will recognize that these ranges(and all ranges listed herein) are provided by way of example and not oflimitation. Further, while there are no formal limits on the dimensionsfor powder metallurgy materials, parts with dimensions of around 100millimeters on each side have been demonstrated to perform well for FFFfabrication of net shape green bodies. Any smaller dimensions may beusefully employed, and larger dimensions may also be employed providedthey are consistent with processing dimensions such as the printresolution and the extrusion orifice diameter. For example,implementations target about a 0.300 μm diameter extrusion, and the MIMmetal powder may typically be about 1˜22 μm diameter, althoughnano-sized powders can be used. The term “metal injection moldingmaterial,” as used herein, is intended to include any such engineeredmaterials, as well as other fine powder bases such as ceramics in asimilar binder suitable for injection molding. Thus, where the termmetal injection molding or the commonly used abbreviation, MIM, is used,this should be understood to include injection molding materials usingpowders other than, or in addition to, metals, and all such materialsare intended to fall within the scope of this disclosure unless adifferent meaning is explicitly provided or otherwise clear from thecontext. Also, any reference to “MIM materials,” “powder metallurgymaterials,” “MIM feedstocks,” or the like shall generally refer to apowder of one or more metals, metal alloys, and/or ceramics mixed withone or more binding materials, e.g., a backbone binder that holdseverything together and a bulk binder that carries the metal andbackbone into position within a mold or print, unless a differentmeaning is explicitly provided or otherwise clear from the context. Itshould also be appreciated that other material systems may be suitablefor fabricating metal parts using fabrication techniques such asstereolithography or binder jetting, some of which are discussed ingreater detail below. As used herein, unless otherwise specified or madeclear from the context, the term “backbone binder” shall be usedinterchangeably with the term “secondary binder,” and the term “bulkbinder” shall be used interchangeably with the term “primary binder.”

In general, fabrication of such materials may proceed as with aconventional FFF process, except that after the net shape is created,the green part may be optionally machined or finished while in a moreeasily workable state, and then debound and sintered into a final, denseobject using any of the methods common in the art for MIM materials. Thefinal object once again may include a metal, a metal alloy, a ceramic,or another suitable combination of materials.

The feedstock 102 may be fed from a carrier 103 to dispense thefeedstock 102 to the three-dimensional printer either in a continuous(e.g., wire) or discrete (e.g., billet) form. The feedstock 102 may, forexample, be supplied in discrete units one by one as billets or the likeinto an intermediate chamber for delivery into the build chamber 116 andsubsequently melted for deposition. In another aspect, the carrier 103may include a spool or cartridge containing the feedstock 102 in anelongate form, such as in the form of a wire. Where a vacuum or othercontrolled environment is desired, the feedstock 102 may be fed througha vacuum gasket into the build chamber 116 in a continuous fashion.Thus, in one aspect, there is disclosed herein an apparatus including aMIM feedstock in the shape of a wire, the feedstock including anengineered composite of metal powder and a polymeric binder or the like,where the carrier 103 may dispense the build material in a continuousfeed to the build chamber 116. For environmentally sensitive materials,the carrier 103 may provide a vacuum environment for the feedstock 102that can be directly or indirectly coupled to the vacuum environment ofthe build chamber 116. More generally, the build chamber 116 (and thecarrier 103) may maintain any suitably inert environment for handling ofthe feedstock 102, such as a vacuum, and oxygen-depleted environment, aninert gas environment, or some gas or combination of gasses that are notreactive with the feedstock 102, where such conditions are necessary orbeneficial for three-dimensional fabrication.

A drive train 104 may include any suitable gears, compression pistons,or the like for continuous or indexed feeding of the feedstock 102 intothe liquefaction system 106. In one aspect, the drive train 104 mayinclude gear shaped to mesh with corresponding features in the feedstock102, such as ridges, notches, or other positive or negative detents. Inanother aspect, the drive train 104 may include heated gears or screwmechanisms to deform and engage with the feedstock 102. Thus, there isdisclosed in one aspect a printer for a fused filament fabricationprocess that heats a feedstock to a working temperature, and that heatsa gear that engages with, deforms, and drives the feedstock in a feedpath. A screw feed may also or instead be used.

For more brittle MIM materials, a fine-toothed drive gear of a materialsuch as a hard resin or plastic may be used to grip the feedstockwithout excessive cutting or stress concentrations that might otherwisecrack, strip, or otherwise compromise the feedstock.

In another aspect, the drive train 104 may include bellows, or any othercollapsible or telescoping press to drive rods, billets, or similarunits of the feedstock 102 into the liquefaction system 106. Similarly,a piezoelectric or linear stepper drive may be used to advance a unit ofthe feedstock 102 in a non-continuous, stepped method with discrete,high-powered mechanical increments. In another aspect, the drive train104 may include multiple stages. In a first stage, the drive train 104may heat the feedstock 102 and form threads or other features that cansupply positive gripping traction into the feedstock 102. In the nextstage, a gear or the like matching these features can be used to advancethe feedstock 102 along the feed path. A collet feed may be used (e.g.,similar to those on a mechanical pencil) in certain instances. A softwheel or belt drive may also or instead be used. In an aspect, a shapeforming wheel drive may be used to ensure accuracy of size and thus thebuild. More generally, the drive train 104 may include any mechanism orcombination of mechanisms used to advance the feedstock 102 fordeposition in a three-dimensional fabrication process. Thus, the term“drive train” should be interpreted in the broadest sense, unless a morespecific meaning is explicitly provided or otherwise clear from thecontext.

The liquefaction system 106 may heat the feedstock 102 to a workingtemperature in a range suitable for extrusion in a fused filamentfabrication process. Any number of heating techniques may be used. Inone aspect, electrical techniques such as inductive or resistive heatingmay be usefully applied to liquefy the feedstock 102. This may, forexample include inductively or resistively heating a chamber around thefeedstock 102 to a temperature at or near the glass transitiontemperature of the feedstock 102, or some other temperature at which abinder or other component of the feedstock 102 becomes workable,extrudable, or flowable for deposition as contemplated herein. Ininstances in which the feedstock 102 is sufficiently conductive, thefeedstock 102 may be directly heated through contact methods (e.g.,resistive heating with applied current) or non-contact methods (e.g.,induction heating using an external electromagnet to drive eddy currentswithin the feedstock 102). The choice of additives for use in thefeedstock 102 may further be advantageously selected to provide bulkelectrical characteristics (e.g., conductance/resistivity) to improveheating. When directly heating the feedstock 102, it may be useful tomodel the shape and size of the feedstock 102 to better controlelectrically-induced heating. The model may, for example, includeestimates or actual measurements of shape, size, mass, etc.

It will also be appreciated that, as used herein, “liquefaction” doesnot require complete liquefaction. That is, the media to be used inprinting may be in a multi-phase state, and/or form a paste or the likehaving highly viscous and/or non-Newtonian fluid properties. Thus, theliquefaction system 106 described herein should be understood to moregenerally include any system that places a feedstock 102 in conditionfor use in fabrication as contemplated herein.

To facilitate resistive heating of the feedstock 102, one or morecontact pads, probes or the like may be positioned within the feed pathfor the feedstock 102 to provide locations for forming a circuit throughthe feedstock 102 at the appropriate location(s). To facilitateinduction heating, one or more electromagnets may be positioned atsuitable locations adjacent to the feed path and operated, e.g., by thecontrol system 118, to heat the feedstock 102 internally through thecreation of eddy currents. In one aspect, both of thesetechniques—resistive heating and inductive heating—may be usedconcurrently to achieve a more tightly controlled or more evenlydistributed electrical heating within the build material. The printer100 may also be instrumented to monitor the resulting heating in avariety of ways. For example, the printer 100 may monitor powerdelivered to the inductive or resistive circuits. The printer 100 mayalso or instead measure temperature of the feedstock 102 and/orsurrounding environment at any number of locations. In another aspect,the temperature of the feedstock 102 may be inferred by measuring, forexample, the amount of force required to drive the feedstock 102 throughthe one or more nozzles 110 or another portion of the feed path. Theforce may be used as a proxy for the viscosity of the feedstock 102.More generally, any techniques suitable for measuring temperature orviscosity of the feedstock 102 and responsively controlling appliedelectrical energy may be used to control liquefaction for a fabricationprocess using composites as contemplated herein.

The liquefaction system 106 may also or instead include any otherheating systems suitable for applying heat to the feedstock 102 to asuitable temperature for extrusion. This may, for example, includetechniques for locally or globally augmenting heating using any one ormore of chemical heating, combustion, ultrasound heating, laser heating,electron beam heating, or other optical, thermal, or mechanical heatingtechniques.

The liquefaction system 106 may include a shearing engine. The shearingengine may create shear within the feedstock 102, as the feedstock 102is heated, to maintain a mixture of the metallic base and a binder orother matrix, or to maintain a mixture of various materials in a pasteor other build material. A variety of techniques may be employed by theshearing engine. In one aspect, the feedstock 102 may be axially rotatedas it is fed along the feed path into the liquefaction system 106. Inanother aspect, one or more ultrasonic transducers may be used tointroduce shear within the heated feedstock 102. Similarly, a screw,post, arm, or other physical element may be placed within the heatedfeedstock 102 and rotated or otherwise actuated to mix the heatedfeedstock 102. In an aspect, the feedstock 102 may include individualpellets, rods, or coils (e.g., of consistent size) and fed into a screw,a plunger, a rod extruder, or the like. For example, the feedstock 102can be initially coiled and can be uncoiled with a heater systemincluding a heated box, heated tube, or another type of heater.

The robotic system 108 may include a robotic system three-dimensionallypositionable to move the one or more nozzles 110 within a working volume115 defined by the build chamber 116. Thus, the robotic system 108 may,for example, include any robotic components or systems suitable forpositioning the one or more nozzles 110 relative to the build plate 114while extruding the feedstock 102 in a pattern to fabricate the object112. A variety of robotics systems are known in the art and suitable foruse as the robotic system 108 contemplated herein. For example, therobotic system 108 may include a Cartesian or x-y-z robotics systememploying a number of linear controls to move independently in thex-axis, the y-axis, and the z-axis within the build chamber 116. Deltarobots may also or instead be usefully employed, which can, in certaininstances, provide significant advantages in terms of speed andstiffness, as well as offering the design convenience of fixed motors ordrive elements. Other configurations such as double or triple deltarobots can increase range of motion using multiple linkages. Moregenerally, any robotics suitable for controlled positioning of the oneor more nozzles 110 relative to the build plate 114, especially within avacuum or similar environment, may be usefully employed including anymechanism or combination of mechanisms suitable for actuation,manipulation, locomotion and the like of the one or more nozzles 110,the build plate 114, or a combination thereof, within the build chamber116.

The one or more nozzle 110 may dispense the feedstock 102 that has beenpropelled with the drive train 104 and, with the liquefaction system106, heated to a suitable working temperature. In a multiphaseextrusion, the working temperature may be above the melting temperatureof a metallic component of the feedstock 102, or more specificallybetween a first temperature at which the metallic component melts and asecond temperature (above the first temperature) at which a second phaseof the feedstock 102 remains inert.

The one or more nozzles 110 may be used to dispense different types ofmaterial. For example, one of the one or more nozzles 110 may dispensethe feedstock 102 while another one of the one or more nozzles 110dispenses a support material to support bridges, overhangs, and otherstructural features of the object 112 that would otherwise violatedesign rules for fabrication with the feedstock 102. In another aspect,the one of the one or more nozzles 110 may deposit different types ofmaterials, such as a thermally compatible polymer or a metal or polymerloaded with fibers of one or more materials, to increase tensilestrength or otherwise improve mechanical properties of the resultingobject 112. In an aspect, two types of supports may be used—(1) buildsupports and (2) sinter supports—e.g., using different materials printedinto the same part to achieve these supports, or to create adistinguishing junction between these supports and the part. In anotheraspect, as described in greater detail below, two or more types offeedstocks may be extruded to form the object 112 with an advantageousspatial distribution to provide targeted structural support of theobject 112 while facilitating rapid debinding of the polymers from theobject 112 to form a dense, final part.

The one or more nozzles 110 may be formed of a material or combinationof materials with mechanical and thermal properties suitable forwithstanding temperatures and forces associated with extrusion of thefeedstock 102. For example, the one or more nozzles 110 will preferablynot degrade at the temperatures at which the feedstock 102 is tdispensed, or due to the passage of particles (e.g., metal, ceramic, orcombinations thereof) through respective dispensing orifices defined bythe one or more nozzles 110. While nozzles for traditional polymer-basedfused filament fabrication may be made from brass or aluminum alloys,the one or more nozzles 110 suitable for dispensing the feedstock 102including a powder material including metal, ceramic, or a combinationthereof may be formed of harder materials, or materials compatible withmore elevated working temperatures such as a high carbon steel that ishardened and tempered. Other materials such as a refractory metal (e.g.molybdenum, tungsten) or refractory ceramic (e.g. mullite, corundum,magnesia) may also or instead be useful to form the one or more nozzles110. In some instances, aluminum nozzles may instead be used for MIMextrusion of certain MIM materials. In another aspect, a softerthermally conductive material with a hard, wear-resistant coating may beused, such as copper with a hard nickel plating.

In one aspect, the nozzle 110 may include one or more ultrasoundtransducers 130 as described herein. Ultrasound may be usefully appliedfor a variety of purposes in this context. In one aspect, ultrasoundenergy from the one or more ultrasound transducers 130 may facilitateextrusion by mitigating clogging (e.g., by reducing adhesion of a buildmaterial to an interior surface of the nozzle 110). A variety of energydirector techniques may be used to improve this general approach. Forexample, a deposited layer may include one or more ridges, which may beimposed by an exit shape of the one or more nozzles 110, to present afocused area to receive ultrasound energy directed from the one or moreultrasound transducers 130 and introduced into an interface between thedeposited layer and an adjacent layer.

In another aspect, the one or more nozzles 110 may include an inductionheating element, resistive heating element, or similar components tocontrol directly a temperature or temperatures of the one or morenozzles 110. This temperature control may augment a more generalliquefaction process along the feed path through the printer 100, e.g.,to maintain a temperature of the feedstock 102 during fabrication.Further, or instead, this temperature control may be used for morespecific functions, such as declogging the one or more nozzles 110 byheating the feedstock 102 substantially above the working range, e.g.,to a temperature where the feedstock 102 is liquid. While it may bedifficult or impossible to control deposition of the feedstock 102 inthis liquid state, the heating can provide a convenient technique toreset the one or more nozzles 110 without more severe physicalintervention such as removing vacuum to disassemble, clean, and replacethe affected components.

In another aspect, the one or more nozzles 110 may include an inlet gasor fan (e.g., an inert gas) to cool media at the moment the media exitsthe one or more nozzles 110. The resulting gas jet may, for example,immediately stiffen the material dispensed from the one or more nozzles110 to facilitate extended bridging, larger overhangs, or otherstructures that might otherwise require support structures underneath.

The object 112 may be any object suitable for fabrication using thetechniques contemplated herein. This may include functional objects suchas machine parts, aesthetic objects such as sculptures, or any othertype of objects, as well as combinations of objects that can be fitwithin the physical constraints of the build chamber 116 and the buildplate 114. Some structures, such as large bridges and overhangs, cannotbe fabricated directly using fused filament fabrication or the likebecause there is no underlying physical surface onto which a materialcan be deposited. In these instances, a support structure 113 may befabricated, preferably of a soluble or otherwise readily removablematerial, to support the corresponding feature.

The one or more nozzles 110 may usefully provide any of a variety ofadditional build materials. This may, for example, include othercomposites, alloys, bulk metallic glasses, thermally matched polymersand so forth to support fabrication of suitable support structures. Bulkmetallic glass particles, for example, may thus be loaded into a MIMfeedstock binder system and may provide a support structure or objectfabrication material. Pure binding or polymer materials (e.g., withoutany loading of a powder material) may also or instead provide a support.A similar metal MIM feedstock may be used for multi-material partcreation. Ceramic or dissimilar metal MIM feedstock may be used for asupport interface material.

In general, the feedstock 102 may include a binder and a powder of amaterial, such as a metal (or other material as described herein). Asupport material may also be provided from a second one of the one ormore nozzles. The support material may consist of, for example, thebinder of the feedstock 102, without the powder of the material that isthermally processable (e.g., sinterable) into the final object. Inanother aspect, the support material may be formed of a wax, or someother thermoplastic or other low molecular weight material that can beremoved during processing of a printed green body. This support materialmay, for example, be used for vertical supports, as well as for top orside supports, or any other suitable support structures to provide aphysical support during printing and subsequent thermal processing ofthe object 112. It will be understood that printing and thermalprocessing may impose different support requirements. As such, differentsupport materials and or different support rules may be employed foreach type of required support. Additionally, the print supports may beremoved after a print and before thermal processing, while thermalprocessing supports are left attached to the green body until thermalprocessing (e.g., sintering) is completed (or sufficiently completed toeliminate or reduce the need for the thermal processing supportstructures).

In another aspect, the second nozzle (or a third nozzle) of the one ormore nozzles 110 may be used to provide an interface material that isdifferent from the support material, such as the corresponding binder,along with a ceramic or some other material that will not sinter underthe time and temperature conditions used to sinter the powder of thematerial in the object 112. The interface material may also or insteadinclude a metal or the like that forms a brittle interface with theobject 112 that has been sintered. The brittle interface can break awayfrom the object 112 that has been sintered to form a final object. Wherethis interface material does not sinter, it may be used in combinationwith a sinterable support structure that can continue to providestructural support to the object 112 during a sintering process.

The support material(s) may usefully integrate other functionalsubstances. For example, titanium may be added to the support materialas an oxygen getter to improve the sintering environment withoutintroducing any titanium into the final object formed by sintering theobject 112. Other types of additives may also or instead be used toremove contaminants. For example, a zirconium powder (or other strongcarbide former) may be added to the support material to extract carboncontamination during sintering of the object 112.

In one aspect, the use of a non-structural support at the interface,e.g. a pure binder that does not sinter into the object 112, may be usedto facilitate the additive manufacture of nested parts. That is, incertain instances, one or more non-structural supports may be removedsuch that the object 112 forms a plurality of parts. For example, theobject 112 may be a complete gear box or the like fabricated within thebuild chamber 116, with the surfaces between gear teeth fabricated witha non-sintering binder or other material. In one aspect, criticalmechanical interfaces for such mechanical parts may be oriented to thefabrication process, e.g., by orienting mating surfaces vertically sothat smaller resolutions can be used. More generally, the capability toprint adjacent, non-coupled parts may be used to fabricate multiplephysically related parts in a single print job. This may, for example,include hinges, gears, captive bearings or other nested or interrelatedparts. Non-sintering support material may be extracted, e.g., using anultrasonicator, fluid cleaning, or other techniques after the object 112is sintered to a final form. In an aspect, the binder is loaded with anon-sintering additive such as ceramic or dissimilar, higher sinteringtemperature metal.

This general approach to providing support structures may also affectthe design of the object 112. For example, fluid paths may be providedin the object 112 for fluid cleaning, and removal paths may be createdin the object 112 for interior support structures. This technique mayalso be used to address other printing challenges. For example, supportstructures within partially enclosed spaces may be fabricated forremoval through some removal path after the object 112 is completed. Ifthe support structures are weakly connected, or unconnected, to theobject 112, the support structures can be physically manipulated forextraction through a removal path. In an aspect, the object 112 mayinclude parts “glued” together with an appropriate (e.g., the same) MIMmaterial to make a larger part that essentially has no joints once theobject 112 is sintered.

The build plate 114 within the working volume 115 of the build chamber116 may include a rigid and substantially planar surface formed of anysubstance suitable for receiving the extrusion of the feedstock 102 fromthe one or more nozzles 110. In one aspect, the build plate 114 may beheated, e.g., resistively or inductively, to control a temperature ofthe build chamber 116 or the surface upon which the object 112 is beingfabricated. Heating the build plate 114 may, for example, improveadhesion, prevent or reduce the likelihood of thermally induceddeformation or failure, and/or facilitate relaxation of stresses withinthe object 112 being fabricated. In another aspect, the build plate 114may be deformable to bend or otherwise physically deform to facilitatedetachment of the build plate 114 from the object 112 formed thereon.

The build chamber 116 may be any chamber suitable for containing thebuild plate 114, the object 112, and any other component or componentsof the printer 100 usefully positioned within the build chamber 116 tofabricate the object 112. In one aspect, the build chamber 116 may be anenvironmentally sealed chamber that can be evacuated with a vacuum pump124 or similar device to provide a vacuum environment in the workingvolume 115 for fabrication of the object 112. This vacuum may beparticularly useful where oxygen results in formation of a passivationlayer that may weaken layer-to-layer bonds in fused filament fabricationprocesses, such as those contemplated herein, or where particles in theatmosphere might otherwise interfere with the integrity of the object112, or where the build chamber 116 is the same as the sinteringchamber. In another aspect, only oxygen is removed from the buildchamber 116.

Similarly, one or more passive or active oxygen getters 126 or othersimilar oxygen absorbing material or system may usefully be employedwithin the build chamber 116 to take up free oxygen within the buildchamber 116. The oxygen getter 126 may, for example, include a depositof a reactive material coating an inside surface of the build chamber116 or a separate object placed within the build chamber 116 thatcompletes and maintains the vacuum by combining with or adsorbingresidual gas molecules. The oxygen getter 126, or more generally, gasgetter, may be deposited as a support material using one of the one ormore nozzles 110, which facilitates replacement of the gas getter witheach new fabrication run and can advantageously position the gasgetter(s) near printed media to improve local removal of passivatinggasses where new material is being deposited onto the object 112. In oneaspect, the oxygen getters 126 may include any of a variety of materialsthat preferentially react with oxygen including, for example, materialsbased on titanium, aluminum, and so forth. In another aspect, the oxygengetters 126 may include a chemical energy source such as a combustiblegas, gas torch, catalytic heater, Bunsen burner, or other chemicaland/or combustion source reactable to extract oxygen from theenvironment. There are a variety of low-CO and NOx catalytic burnersthat may be suitably employed for this purpose.

In one aspect, the oxygen getter 126 may be deposited as a separatematerial during a build process. Thus, in one aspect, fabricating theobject 112 from the feedstock 102 may include co-fabricating aphysically adjacent structure (which may or may not directly contact theobject 112) containing an agent to remove passivating gasses around theobject 112. Other techniques may be similarly employed to controlreactivity of the environment within the build chamber 116, or withinone or more post-processing chambers or the like as described below. Forexample, the build chamber 116 may be filled with an inert gas or thelike to prevent or reduce the likelihood of oxidation of materialforming the object 112 and/or other material present in the buildchamber 116.

The control system 118 may include a processor and memory, as well asany other co-processors, signal processors, inputs and outputs,digital-to-analog or analog-to-digital converters and other processingcircuitry useful for monitoring and controlling a fabrication process(such as, for example, any one or more of the additive manufacturingprocesses described herein) executing on the printer 100. The controlsystem 118 may be coupled in a communicating relationship with a supplyof the feedstock 102, the drive train 104, the liquefaction system 106,the one or more nozzles 110, the build plate 114, the robotic system108, and any other instrumentation or control components associated withthe build process, such as temperature sensors, pressure sensors, oxygensensors, vacuum pumps, and so forth. The control system 118 may beoperable to control the robotic system 108, the liquefaction system 106and other components to fabricate the object 112 from the feedstock 102by extruding the feedstock 102 through tone one or more nozzles 110 inthree dimensions within the working volume 115 of the build chamber 116.

The control system 118 may generate machine ready code for execution bythe printer 100 to fabricate the object 112 from a three-dimensionalmodel 122. The control system 118 may deploy a number of strategies toimprove the resulting physical object structurally or aesthetically. Forexample, the control system 118 may use plowing, ironing, planing, orsimilar techniques where the one or more nozzles 110 run over existinglayers of deposited material, e.g., to level the material, removepassivation layers, apply an energy director topography of peaks orridges to improve layer-to-layer bonding, or otherwise prepare thecurrent layer for a next layer of material. The one or more nozzles 110may include a low-friction or non-stick surface such as Teflon, TiN orthe like to facilitate this plowing process. Further, or instead, theone or more nozzles 110 may be heated and/or vibrated (e.g., using anultrasound transducer) to improve the smoothing effect. In one aspect,surface preparation may be incorporated into the initially-generatedmachine ready code. In another aspect, the printer 100 may dynamicallymonitor deposited layers and determine, on a layer-by-layer basis,whether additional surface preparation is necessary or helpful forsuccessful completion of the object 112.

In one aspect, pressure or flow rate may be a process feedback signal tothe control system 118. While temperature is frequently a criticalphysical quantity for fabrication with certain materials, it may bedifficult to accurately measure the temperature of a composite buildmaterial, such as the feedstock 102, throughout a feed path. However,the temperature can be inferred by the viscosity of the feedstock 102,which can be estimated for the bulk material based on how much force isbeing applied to drive the feedstock 102 through a feed path. Thus, inone aspect, the printer 100 may measure the force applied by the drivetrain 104 to the feedstock 102, infer a temperature of the feedstock 102based on the instantaneous force, and control the liquefaction system106 to adjust the temperature accordingly.

In general, the three-dimensional model 122 of the object 112 may bestored in a database 120, such as a local memory of a computer used asthe control system 118, or a remote database accessible through a serveror other remote resource, or in any other computer-readable mediumaccessible to the control system 118. The control system 118 mayretrieve the three-dimensional model 122 (e.g., a particular model) inresponse to user input, and generate machine-ready instructions forexecution by the printer 100 to fabricate the object 112 correspondingto the three-dimensional model 122. Generating machine-readyinstructions may include the creation of intermediate models, such aswhere a CAD model is converted into an STL model or other polygonal meshor other intermediate representation, which can, in turn, be processedto generate machine instructions for fabrication of the object 112 bythe printer 100.

In another aspect, the one or more nozzles 110 may include one or moremechanisms to flatten a layer of deposited material and apply pressureto bond the layer to an underlying layer. For example, a heated niproller, caster, or the like may follow the one or more nozzles 110 asthe one or more nozzles 110 move along respective one or more pathsthrough an x-y plane of the build chamber 116 to flatten the deposited(and still pliable) layer of extruded material. The one or more nozzles110 may also or instead integrate a forming wall, planar surface or thelike to additionally shape or constrain the feedstock 102 as it extrudedthrough the one or more nozzles 110. The one or more nozzles 110 mayusefully be coated with a non-stick material (which may vary accordingto the build material being used) to facilitate more consistent shapingand smoothing by the one or more nozzles 110 in instances in which theone or more nozzles 110 are used for these purposes.

In another aspect, the printer 100 may include a layer fusion system 132useful for encouraging good mechanical bonding between adjacent layersof the feedstock 102 deposited within or along the object 112. The layerfusion system 132 may include the ultrasound transducers describedabove, which may be used to facilitate bonding between layers byapplying ultrasound energy to an interface between layers duringdeposition. In another aspect, the layer fusion system 132 may passcurrent through an interface between adjacent layers to Joule heat theinterface and liquefy or soften the materials of the adjacent layers forimproved bonding between the adjacent layers. Thus, in one aspect, thelayer fusion system 132 may include a joule heating system positionableto apply a current between a first layer of the feedstock 102 extrusionand a second layer of the feedstock 102 extrusion in the working volume115 while the first layer is being deposited on the second layer. Inanother aspect, the layer fusion system 132 may include an ultrasoundsystem for applying ultrasound energy to a first layer of the feedstock102 extrusion while the first layer is being deposited onto a secondlayer of the feedstock 102 extrusion in the working volume 115. Inanother aspect, the layer fusion system 132 may include a rake,ridge(s), notch(es) or the like formed into the end of the one or morenozzles 110, or a fixture or the like adjacent to the one or morenozzles, to form energy directors on a top surface of the extrudedfeedstock 102. Other techniques may also or instead be used to improvelayer-to-layer bonding, such as plasma cleaning or other depassivationbefore or during formation of the interlayer bond.

During fabrication, detailed data may be gathered for subsequent use andanalysis. For example, the printer 100 may include a camera and computervision system that identifies errors, variations, or the like that occurin each layer of the object 112. Similarly, tomography or other imagingtechniques may be used to detect and measure layer-to-layer interfaces,aggregate part dimensions, diagnostic information (defects, voids, andthe like) and so forth. These data may be gathered and delivered withthe object 112 to an end user as a digital twin 140 of the object 112 sothat the end user can evaluate whether and how variations and defectsmight affect use of the object 112. In addition to spatial/geometricanalysis, the digital twin 140 may log process parameters including,e.g., aggregate statistics such as weight of material used, time ofprint, variance of build chamber temperature, and so forth, as well aschronological logs of any process parameters of interest such asvolumetric deposition rate, material temperature, environmenttemperature, and so forth.

The printer 100 may include a camera 150 or other optical device. In oneaspect, the camera 150 may be used to create the digital twin 140described above, or to more generally facilitate machine visionfunctions or facilitate remote monitoring of a fabrication process.Video or still images from the camera 150 may also or instead be used todynamically correct a print process, or to visualize where and howautomated or manual adjustments should be made, e.g., where an actualprinter output is deviating from an expected output.

The printer 100 may include a subtractive fabrication tool 160 such as adrill, milling bit, or other multi-axis controllable tool for removingmaterial from the object 112. For example, the subtractive fabricationtool 160 may remove from the object 112 material that deviates from anexpected physical output based on the three-dimensional model 122 usedto fabricate the object 112. The use of MIM materials such as thefeedstock 102 provides an advantage when subtractive shaping isperformed on the object 112 as a green body (e.g., after net shapeforming but before thermal processing (or debinding)), when the object112 is relatively soft and workable. More specifically, the use of MIMmaterials to form the object 112 permits quick and easy removal ofphysically observable defects and printing artifacts before the object112 is sintered or otherwise thermally processed into a dense, finalobject. Further, or instead, the subtractive fabrication tool 160 may beoperable to tap threads or otherwise add features to the object 112.Similarly, an aspect may include combining multiple single green partsinto one larger fully solid sintered part.

Other useful features may be integrated into the printer 100 describedabove. For example, a solvent or other material may be usefully applieda surface of the object 112 during fabrication to modify properties ofthe object 112. The solvent may, for example, intentionally oxidize orotherwise modify a surface of the object 112 at a particular location orover a particular area to provide a desired electrical, thermal,optical, or mechanical property. This capability may be used to provideaesthetic features such as text or graphics, or to provide functionalfeatures such as a window for admitting RF signals.

In general, a fabrication process such as FFF implies, or expresslyincludes, a set of design rules to accommodate physical limitations of afabrication device and a build material. For example, a horizontal shelfcannot generally be fabricated without positioning a support structureunderneath. While the design rules for FFF apply to fabrication of agreen body using FFF techniques as described herein, the green body mayalso be subject to various MIM design rules. This may, for example,include a structure to prevent or minimize drag on a floor while a partshrinks during sintering which may be 20% or more depending on thecomposition of the green body. Similarly, certain supports are requiredduring sintering, and these supports may be different than the supportsrequired during FFF. As another example, injection molding typicallyaims for uniform wall thickness to reduce variability in debindingand/or sintering behaviors, with thinner walls being preferred. Theprinter 100 may apply disparate sets of design rules—those for the rapidprototyping system (e.g., FFF) and those for the sintering process(e.g., MIM design rules)—to a CAD model that is being prepared forfabrication of the object 112.

The FFF design rules and the MIM design rules may also be combined undercertain conditions. For example, the support structures for a horizontalshelf during fabrication must resist the force of anextrusion/deposition process used to fabricate the horizontal shelf,whereas the support structure during sintering only needs to resist theforces of gravity during the baking process. Thus, the CAD model forfabrication of the object 112 may include two separate supports that areremovable at different times during a fabrication process: fabricationsupports that are configured to resist the force of a fabricationprocess and may be breakaway supports that are loosely mechanicallycoupled to a green body, along with sintering supports that may be lessextensive, and only need to resist the gravitational forces on a bodyduring sintering. These latter supports may be preferably coupled to theobject 112 through a non-sinterable layer to facilitate easy removalfrom the dense, final object. In another aspect, the fabricationsupports may be fabricated from binder without a powder or other fill sothat the fabrication supports may completely disappear during asintering process.

FIG. 2 is a flow chart of an exemplary method 200 for printing athree-dimensional object with composites, e.g., metal injection moldingmaterials.

As shown in step 202, the exemplary method 200 may include providing abuild material including an injection molding material, or where asupport interface is being fabricated, a MIM binder (e.g., a MIM binderwith similar thermal characteristics). The material may, for example, beany of the MIM materials contemplated herein. The material may beprovided as a feedstock in a billet, a wire, or any other cast, drawn,extruded or otherwise shaped bulk form. As described above, thefeedstock may be further packaged in a cartridge, spool, or othersuitable carrier that can be attached to an additive manufacturingsystem for use.

As shown in step 204, the exemplary method 200 may include fabricating alayer of an object in a working volume of a build chamber. This mayinclude any techniques that can be adapted for use with MIM materials.For example, this may include fused filament fabrication, jet printing,selective laser sintering, or any other techniques for forming a netshape from a MIM material (and more specifically for techniques used forforming a net shape from a polymeric material loaded with a powder of amaterial in a second phase).

As shown in step 211, exemplary method 200 may be continued and repeatedas necessary to fabricate an object within the working volume. While theprocess may vary according to the underlying fabrication technology, anobject can generally be fabricated layer by layer based on athree-dimensional model of the object being fabricated.

As shown in step 212, the exemplary method 200 may include shaping thenet shape object after the additive process is complete. Beforedebinding or sintering, the green body form of the object is usefully ina soft, workable state where defects and printing artifacts can beremoved, either manually or automatically, rather easily as compared toremoval from a harder form of the object. Thus, the exemplary method 200may take advantage of this workable, intermediate state to facilitatequality control or other process-related steps, such as removal ofsupports that are required for previous printing steps, but not requiredfor debinding or sintering.

As shown in step 214, the exemplary method 200 may include debinding theprinted object. In general, debinding may be performed chemically orthermally to remove a binder that retains a powder of a material (e.g.,a metal, a metal alloy, and/or a ceramic) in a net shape. Contemporaryinjection molding materials are often engineered for thermal debinding,which advantageously permits debinding and sintering to be performed ina single thermal operation, or in two similar thermal operations. Ingeneral, the debinding process may remove binder from the net shapegreen object, leaving a dense structure of the material of the powderthat can be densified (e.g., through sintering, infiltration with aliquid metal, or other thermal processing) into the final form.

As shown in step 216, the exemplary method 200 may include densifyingthe printed and debound object into a final form. For the sake ofefficient and clear description, the printed and debound object mayoccasionally be referred to herein as a brown part. In general,densifying the brown part may include applying to the brown part anyprocess of compacting and forming a solid mass of material withoutliquefaction. Thus, densification of the brown part may include any oneor more thermal processes, such as sintering, infiltration of the objectwith a liquid metal, and combinations thereof. For example, during asintering process, atoms can diffuse across particle boundaries to fuseinto a solid piece. Because sintering can be performed at temperaturesbelow the melting temperature of the metal, sintering can advantageouslyfacilitate fabrication with high melting point materials, examples ofwhich include tungsten and molybdenum.

Numerous sintering techniques are known in the art, and the selection ofa particular sintering technique may depend upon the composition of thebrown part, and the desired structural, functional or aesthetic resultfor the final object. For example, in solid-state (non-activated)sintering, metal powder particles are heated to form connections (or“necks”) where they are in contact. Over time, these necks thicken andcreate a dense part, leaving small, interstitial voids that can beclosed, e.g., by hot isostatic pressing (HIP) or similar processes.Other techniques may also or instead be employed. For example, solidstate activated sintering uses a film between powder particles toimprove mobility of atoms between particles and accelerate the formationand thickening of necks. As another example, liquid phase sintering maybe used, in which a liquid forms around metal particles. This canimprove diffusion and joining between particles, but also may leave alower-melting phase within the sintered object that may impairstructural integrity. Other advanced techniques such as nano-phaseseparation sintering may be used, for example to form a high-diffusivitysolid at the necks to improve the transport of metal atoms at thecontact point, as described for example in “Accelerated sintering inphase-separating nanostructured alloys,” Park et al., NatureCommunications, 6:6858 (DOI: 10.1038/ncomms7858) (Apr. 22, 2015),incorporated herein by reference in its entirety.

It will be understood that debinding and thermal processing may resultin material loss and compaction, and the resulting object may besignificantly smaller than the printed object. However, these effectsare generally linear in the aggregate, and net shape objects can beusefully scaled up when printing to create a target shape afterdebinding and sintering.

FIG. 3 is a schematic representation of an additive manufacturing system300 for use with metal injection molding materials, such as any one ormore of the metal injection molding materials described herein, unlessotherwise indicated or made clear from the context. The additivemanufacturing system 300 may include a printer 302, a conveyor 304, anda post-processing station 306.

In general, the printer 302 may be any of the printers described hereinincluding, for example, the printer 100 (FIG. 1). More generally, theprinter 302 may be a fused filament fabrication system, astereolithography system, a selective laser sintering system, or anyother system that can be usefully adapted to form, under computercontrol, a net shape object using injection molding materials. Theoutput of the printer 302 may be an object 303 which, unless otherwiseindicated or made clear from the context, shall be understood to besimilar to the object 112 (FIG. 1). Thus, for example, the object 303may be a green body including any suitable powder of a material (e.g.,metal, metal alloy, ceramic, and so forth, as well as combinations ofthe foregoing), along with one or more binders that retain the powder ina net shape produced by the printer 302.

The conveyor 304 may transport the object 303 from the printer 302 to apost-processing station 306, where debinding and thermal processing(e.g., sintering) can be performed. The conveyor 304 may be any suitabledevice or combination of devices suitable for physically transportingthe object 303. This may, for example, include robotics and a machinevision system or the like on the printer side for detaching the object303 from a build platform or the like, as well as robotics and a machinevision system or the like on the post-processing side to accuratelyplace the object 303 within the post-processing station 306. In anotheraspect, the post-processing station 306 may serve multiple printers sothat a number of objects can be debound and thermally processedconcurrently, and the conveyor 304 may interconnect the printers andpost-processing station so that multiple print jobs can be coordinatedand automatically completed in parallel. In another aspect, the object303 may be manually transported between the two corresponding stations.

The post-processing station 306 may be any system or combination ofsystems useful for converting a green part—formed into a desired netshape from a metal injection molding build material by the printer302—into a final object. The post-processing station 306 may, forexample, include a chemical debinding station and a thermal sinteringstation that can be used in sequence to produce a final object. Somecontemporary injection molding materials are engineered for thermaldebinding, which makes it possible to perform a combination of debindingand sintering steps with a single oven or similar device. While thethermal specifications of a sintering furnace will depend upon thepowder to be sintered, the binder system, the loading, and other aspectsof the green object and the materials used to manufacture same,commercial sintering furnaces for thermally debinding and sintering MIMparts typically operate with an accuracy of +/−5 degrees Celsius orbetter, and at temperatures of at least 600 degrees C., or from about200 degrees C. to about 1900 degrees C. for extended times. Any suchfurnace or similar heating device may be usefully employed as part ofthe post-processing station 306 as contemplated herein. Vacuum orpressure treatment may also or instead be used. In an aspect, identicalor similar material beads with a non-binding coating may be used for afurnace support—e.g., packing in a bed of this material that shrinkssimilar to the part, except that it will not bond to the part.

It will also be appreciated that a wide range of other debinding andthermal processes can be used. For example, all or a portion of a bindersystem may be removed in a chemical debind, a thermal debind, or somecombination of these. Other debinding processes are also known in theart (such as supercritical or catalytic debinding), any of which mayalso or instead be employed by the post-processing station 306 tothermally process the object 303 as contemplated herein. For example, ina common process, a green part is first debound using a chemical debind,which is followed by a thermal debind at a moderately high temperature(in this context, around 700-800 C) to remove organic binder and createenough necks among a powdered material to form a brown part that may behandled. From this stage, the object may be moved to a sintering furnaceto remove any remaining components of a binder system and densify theobject. In another aspect, a pure thermal debind may be used to removethe organic binder. More general, any technique or combination oftechniques may be usefully employed to debind an object as contemplatedherein.

Similarly, a wide range of sintering techniques may be usefully employedby the post-processing station 306. In one aspect, the object 303 may beconsolidated in a furnace to a high theoretical density using vacuumsintering. In another aspect, the furnace may use a combination offlowing gas (e.g., at below atmospheric pressure, slightly aboveatmospheric pressure, or some other suitable pressure) and vacuumsintering. More generally, any sintering or other process suitable forimproving object density may be used, preferably such that the processyields a near-theoretical density part with little or no porosity.Hot-isostatic pressing (“HIP”) may also (e.g., as a post-thermalprocessing finishing step) or instead be employed, e.g., by applyingelevated temperatures and pressures of 10-50 ksi, or between about 15and 30 ksi. In another aspect, the object 303 may be processed using anyof the foregoing, followed by a moderate overpressure (greater than thesintering pressure, but lower than HIP pressures). In this latterprocess, gas may be pressurized at 100-1500 psi and maintained atelevated temperatures within the furnace or some other supplementalchamber. In another aspect, the object may be separately heated in onefurnace, and then immersed in a hot granular media inside a die, withpressure applied to the media so that the pressure can be transmitted tothe object 303 to drive more rapid consolidation to near full density.More generally, any technique or combination of techniques suitable forremoving binder systems and driving a powdered material towardconsolidation and densification may be used by the post-processingstation 306 to process a fabricated green part as contemplated herein.

In one aspect, the post-processing station 306 may be incorporated intothe printer 302, thus removing a need to physically transport the object303, such as via the conveyor 304. The build volume of the printer 302and components therein may be fabricated to withstand the elevatedtemperatures during debind and/or thermal processing. In another aspect,the printer 302 may provide movable walls, barriers, or otherenclosure(s) within the build volume so that the debind and/or sintercan be performed while the object 303 is on a build platform within theprinter 302, but thermally isolated from thermally sensitive componentsor materials.

The post-processing station 306 may be optimized in a variety of waysfor use in an office or similar interior environment. In one aspect, thepost-processing station 306 may include an inert gas source 308. Theinert gas source 308 may, for example, include argon or other inert gas(or other gas that is inert with respect to the sintered material), andmay be housed in a removable and replaceable cartridge that can becoupled to the post-processing station 306 for discharge into theinterior of the post-processing station 306, and removed and replaced(e.g., when the contents are exhausted). The post-processing station 306may also or instead include a filter 310 such as a charcoal filter orthe like for exhausting gasses that can be outgassed into an officeenvironment in an unfiltered form. For other gasses, an exteriorexhaust, or a gas container or the like may be provided to permit use inunventilated areas. For reclaimable materials, a closed system may alsoor instead be used, particularly where the environmental materials areexpensive or dangerous.

In one aspect, the post-processing station 306 may be coupled to othersystem components. For example, the post-processing station 306 mayinclude information from the printer 302, or from a controller for theprinter, about the geometry, size, mass and other physicalcharacteristics of the object 303 to generate a suitable debinding andthermal processing profile. In another aspect, the profile may beindependently created by the controller or other resource andtransmitted to the post-processing station 306 when the object 303 isconveyed. In another aspect, the post-processing station 306 may monitorthe debinding and thermal process and provide feedback, e.g., to aremote device 312 (e.g., a smart phone), about a status of the object, atime to completion, and other processing metrics and information. Thepost-processing station 306 may include a camera 314 or other monitoringdevice to provide feedback to the remote device 312, and may providetime lapse animation or the like to graphically show sintering or otherthermal processing on a compressed time scale. Post-processing may alsoor instead include finishing with heat, a hot knife, tools, or similartechniques. Post-processing may, further or instead, include applying afinish coat.

In one aspect, the post-processing station 306 may employ microwavesintering to accelerate post processing. Powdered metals in particularare good absorbers of microwave energy and can be efficiently heatedusing microwave techniques. Ceramics can also be sintered in thismanner, where microwave heating is linked to the dielectric loss of thematerial and other factors. A suitable microwave sintering process isdescribed for example in Agrawal, “Microwave sintering of ceramics,composites, metals, and transparent materials,” Journal of MaterialsEducation, Vol. 19, pp. 49-47, incorporated herein by reference in itsentirety, where microwave sintering times were reduced, e.g., from 12-24hours down to 90 minutes, with comparable density, hardness, and bendingstrength of the sintered material. Any other configuration suitable formicrowave heating in an amount and for a duration suitable for sinteringof MIM materials may also or instead be employed.

Where the binder system of the feedstock is also engineered for thermaldebinding, the method may include debinding the green object by applyingmicrowave energy, e.g., using the post-processing station 306 describedabove.

FIG. 4 is a schematic representation of a stereolithography processusing a powder of material and a curable binder. In general, a buildmaterial 402 may be formed using an injection molding powder, such asany of those described herein, dispersed in a curable binder. Thecurable binder may be any suitable photopolymer resin curable using alight source compatible with curing the binder. For example, a laser 404may be used to provide light at a specific wavelength suitable forcuring the binder. More specifically, in instances in which the buildmaterial 402 includes a UV-curable binder, the laser 404 may provide UVlight such that exposure of the build material 402 to light from thelaser 404 may cure the UV-curable binder. The build material 402 may becured on a layer-by-layer basis with the laser 404 using knownstereolithography techniques to form a cured green body having a shapeof the desired object. It will be appreciated that MIM powders willgenerally be opaque, and adaptations to a light source of the laser 404may be used to improve the structural integrity of the fabricated greenobject, such as forming a layer size equal to or less than an averagediameter of powder particles suspended in the build material 402, orproviding laser light from multiple sources/directions to reduce orminimize occlusion of the resin at each layer. In another aspect, thereis disclosed herein a sinterable, net shape green body object formedaccording to a computer model and including a base material in powderform and a curable (or cured) resin that can be debound and/or thermallyprocessed into a final object, as well as a process for sintering anobject comprising a base material in powder form and a cured resin. Itshall be understood that the powder may be suspended within a curablebinder, creating a slurry or suspension. The mass and surface area ofthe particles versus the specific rheology of the binder may dictatewhether or not the powder will float indefinitely or settle due togravity. Using nano sized particles may optimize the ability of thepowder to form a stable suspension that does not settle (over reasonabletimescales).

To reduce binder char and subsequent carbon contamination and increaseshape retention, the binder may include two parts—a curable resin (e.g.,a UV curable resin) and a second component that may be removed (e.g.,debound) prior to moving the object into a furnace. Similarmulticomponent binder formulations have been shown to reduce carbonpickup from the burnout process and reduce part failures by buildup ofgases inside the part. Many possible binder combinations exist,including poly(ethylene glycol) (PEG) as a solvent-soluble primarybinder component that may be removed prior to insertion of the objectinto the furnace, along with a secondary binder based on poly(ethyleneglycol) diacrylate (PEG-DA), or any number of other curable resins.

The curable resin may be a UV curable resin, such as a commerciallyavailable investment casting resin engineered for stereolithographyfabrication, or any other suitable curable resin or the like. The UVcurable resin may usefully incorporate an increased concentration of anactivating die (at least 50% greater than typical commercially availableUV curable resins) to compensate for optical interference of opaqueparticles.

In another aspect, the stereolithography process may be modified toaddress particle opacity in other ways. For example, a current layer maybe coated with a polymer (e.g., by moving the object along the z-axiswithin a bath 406, either up or down according to the species ofstereolithography being employed), and then a powder may be introduced,after which the layer may be cured in a desired cross section usingexposure to light of an appropriate wavelength. In another aspect, thelayer may be cured, powdered, and then coated with another layer ofpowder, so that the resin is fully exposed to the light stimulus beforecoating with an additional powder layer.

In another aspect, the mixture of a MIM powder and a curable resin maybe dispensed and cured (e.g., photocured) on a layer-by-layer basis toremove or reduce the need for the bath 406.

Further, or instead, any technique for local thermal activation of abinder may be used in combination with a powder bed of MIM material (andbinder) as contemplated herein to form a green body. For example,targeted thermal activation may be achieved with a thermal print head,an IR heating mask and/or lamp, focused microwave energy, selectivethermal sintering, steering of an activation beam with a digital lightprocessing chip, a heated roller, or any other technique or combinationof techniques. For example, a variety of thermal print heads arecommercially available, e.g., from KYOCERA® and other manufacturers thatmay be suitably adapted to applying targeted thermal energy to a layerof binder and MIM powder.

FIG. 5 is a schematic representation of a laser binding process forpowder metallurgy materials. In a process similar to selective lasersintering, a powder/binder mixture 501 may be fed from a powder deliverysystem 502 to a fabrication bed 504. The binder in the powder/bindermixture 501 may be activated on a layer-by-layer basis using anactivation source 506 (e.g., a laser) to create a low strength bond inthe binder in the powder/binder mixture for each cross section of atarget shape. This activation may form a sufficient bond to retain thepowder/binder mixture in a net shape green body 508 that can be removedand thermally processed using one or more of thermal processes describedherein. Suitable binders are available that can be activated usingrelatively inexpensive, low-power, fast laser processes or masked IR orUV. Such binders significantly improve upon existing direct metal lasersintering processes that otherwise require special atmospheric controlsand high-power lasers.

Higher energy lasers may be usefully employed, for example, to morefully melt and/or remove binder material and improve the density of thegreen body before sintering, or to initiate sintering of the metalwithin the green body. In another aspect, the MIM materials contemplatedherein may be adapted for use in a selective laser melting process wherethe binder melts to form a net-shape green body which is then deboundand sintered according to the methods described herein.

FIG. 6 is a schematic representation of the use of finishing materialsin a fabricated object. In general, the particle size of the powder usedin a FFF build material or the like may affect the available printresolution and surface finish of the object 600. To address this issue,a low-resolution material 602 may be used to fabricate internalstructures of the object 600, and a high-resolution material 604 may beused to fabricate surface structures.

The low-resolution material 602 may contain larger particle sizes (e.g.,about 10-20 microns) suitable for the generally larger feature size andprint resolution used to fabricate the interior of the object. Thehigh-resolution material 604 may include smaller particle sizes (e.g.,less than 10 microns, or less than one micron). The high-resolutionmaterial 604 may take longer to print, and may be more expensive,particularly where very small and more difficult to fabricate particlesare incorporated into the build material. Thus, it may be beneficial,both in terms of fabrication time and fabrication cost, to limit the useof high resolution materials to the exterior surfaces. To preventcollisions of a print tool with the printed object 600, it may also beuseful to print exterior surface first up to a layer height of thelow-resolution material 602, after which a road of the low-resolutionmaterial may be added. The materials may, e.g., be deposited fromdifferent nozzles, or from a variable sized nozzle, preferably withappropriate purging operations between materials.

Thus, there is disclosed herein a printer that uses a low-resolutionfeedstock for interior structures and a high-resolution feedstock forexterior structures. While a side structure is shown for the sake ofclarity of illustration, it will be appreciated that the high-resolutionfeedstock can be, further or instead, advantageously used for otherstructures such as floors, roofs, and other structures within an object.

FIG. 7 is a perspective view of drive wheels 702, 704 suitable fordriving a MIM feedstock in a FFF process. While the drive wheels 702,704 provide adequate traction and drive for MIM feedstock using variousbinder systems including wax, thermoplastics, and so forth, the drivewheel 704 provides right angled gripping surfaces for greater engagementwith the feedstock, as well as more convenient manufacturing (e.g.,using a rope knurling process or the like) than the rounded engagementsurfaces of the drive wheel 702.

In the field of metal injection molding, materials have high metalloading (e.g., >50% by volume, where greater metal loading can improveand accelerate sintering) and good flow properties at elevatedtemperatures. The properties of metal injection molding (or “MIM”, orsometimes “PIM” when referring to powder metallurgy injection molding)materials are different, however, from those of paste-based materialsknown for use in extruding sinterable objects. It is believed that,because of these differences in properties, MIM materials have not beenused in print-style fabrication of a green body or, more particularly,in FFF-type extrusion of green body material. The applicants havedetermined that a variety of commercially available MIM compositions maybe usefully employed as a feedstock for fused filament fabrication.Significantly, while the particle sizes of 50 microns or more are notwell-suited for use with existing FFF parts (e.g., nozzles with an exitdiameter of 400 microns or less), solid rods of MIM material having alower particle size have been demonstrated to extrude well using aconventional FFF machine with an extrusion diameter of 400 microns and abuild material temperature of about 200 degrees Celsius. Nozzles havebeen fabricated and employed for these feedstocks using, e.g., adiameter ranging from about 400 microns to about 250 microns, and havingan exit diameter near or between these values.

In general, a base powder may be formed of any powder metallurgymaterial. While the particular process, e.g., fused filament fabricationor stereolithography, may impose dimensional constraints or preferences,it appears that smaller particles are generally preferable. Varioustechniques have been developed for mass producing fine metal powders foruse in MIM processes. In general, powders may be prepared by crushing,grinding, gas atomization, chemical reactions, electrolytic deposition,or combinations thereof. Any such powders from 1 to 20 microns in sizemay be used as the base powder of a MIM material as contemplated herein.Smaller particles may also be used where they are available and notprohibitively expensive. Further, or instead, larger particles may beused, provided that such larger particles are compatible with printresolution and physical hardware (e.g., an exit nozzle diameter) of afabrication device.

MIM powders including stainless steel, titanium, titanium alloys,high-nickel alloys, nickel copper alloys, magnetic alloys, and the likeare commercially available. Powders of the elements titanium, vanadium,thorium, niobium, tantalum, calcium, and uranium have been produced byhigh-temperature reduction of the corresponding nitrides and carbides.Iron, nickel, uranium, and beryllium submicrometer powders have beendemonstrated by reducing metallic oxalates and formates. Exceedinglyfine particles also have been prepared by directing a stream of moltenmetal through a high-temperature plasma jet or flame, to atomize thematerial. Various chemical and flame powdering processes may be used inpart to prevent serious degradation of particle surfaces by atmosphericoxygen. More generally, any technique suitable for producing powderedmetals or other materials for use in printing as contemplated herein maybe adapted for the fabrication of a base powder. As a significantadvantage, these techniques permit the processing and use of relativelyhigh melting temperature metals at the significantly lower temperaturesrequired for sintering. Thus, for example, powders of tungsten or steelalloys can be usefully sintered at temperatures below 700 degreesCelsius.

Binders may generally support a net shape after initial fabricationthrough sintering. In contemporary MIM materials, a binder system mayinclude multiple binders that can be generally classified as primarybinders (or, sometimes bulk binders) and secondary binders (or,sometimes, backbone binders). The primary binder can flow at elevatedtemperatures, and retain the shape of an object after an initial build(e.g., in normal atmospheric conditions). The secondary binder providesbinding later into the sintering process and helps retain the shape ofthe object as the sintering progresses. The secondary binder(s) will bethe last to gas off during a sintering process. The binder system mayvary according to the intended application. For example, the bindersystem may be formed of polymers with a lower glass transitiontemperature or less viscosity for higher-resolution printing.

In general, binder systems for commercially available MIM materials arenot engineered for use in fused filament fabrication processes. Forexample, these commercially available MIM materials include polymermixes that are brittle at room temperature and, thus, generallyunsuitable for extrusion in a fused filament fabrication process. In oneaspect, feedstocks of the present disclosure may include a polymerbinder system that is flexible at room temperature to facilitate formingthe feedstock into a filament that can be, for example, wound onto aspool for extended, continuous feeding to a printer. Also, traditionalMIM feedstocks may include many different additives, such as lubricantsand release oils, to help injection molded parts through the moldingprocess. However, these additives may not be desired for fused filamentfabrication applications. Thus, additives used in traditional MIMfeedstock may be replaced with components that make the feedstock moreprintable in fused filament fabrication.

The binder systems described herein may also or instead usefully beadapted for use with ceramic powders or other materials. The rheology ofthe extrudate is largely independent of the material loaded into thebinder system, and depends more on particle geometry of the powder thanon particle composition. As such, any reference to metal injectionmolding, MIM, or MIM materials should be understood to include ceramics,metal oxides, and other powders in a MIM-style binder system, unless adifferent meaning is expressly stated or otherwise clear from thecontext.

Other additives may also or instead be included in feedstocks describedherein. For example, the feedstock may incorporate a getter for oxygenor other contaminants as described above, particularly when used as asupport material. As another example, the feedstock may include a phasethat is liquid at sintering temperatures, or some other surface-activeadditive to accelerate the sintering process.

A variety of engineered materials have been developed using powders andbinders suitable for, e.g., die pressing or similar injection moldingtechniques. The applicants have found, through experimentation, thatcertain injection molding materials have suitable physical and thermalcharacteristics for use with a conventional fused filament fabricationmachine, which can be used to form green bodies from the MIM materialsuitable for debinding and sintering.

In the discussion that follows, various different adaptations of MIMmaterials are described, with these adaptations generally addressing thechallenges of using MIM materials as feedstock for rapidly forming partsthrough extrusion-based additive manufacturing techniques, such as fusedfilament fabrication. For example, feedstocks of the present disclosuremay include a composite feedstock useful for achieving desiredproperties or, in certain cases, variations in properties in a feedstockand/or in a three-dimensional object formed through extrusion of thefeedstock. As another example, feedstocks of the present disclosure mayinclude an aggregate of low molecular weight polymers in a physicallycrosslinked relationship to one another, with such an aggregate of lowmolecular weight polymers facilitating bending (e.g., spooling) thefeedstock while the physically crosslinked relationship may bereversible in a solvent to facilitate debinding. As yet another example,feedstocks of the present disclosure may include a primary binderincluding a high molecular weight polymer component useful for achievinghigh print quality and strength of a three-dimensional object whilebeing chemically decomposable (e.g., depolymerizable) or dissolvable ina solvent for rapid debinding. As still another example, feedstocks ofthe present disclosure may be combined to form a part including aspatial gradient of a first primary binder and a second primary binder,the first primary binder and the second primary binder having differentproperties such that the spatial gradient forms a three-dimensionalobject having an advantageous combination of adequate structural supportwhile also having a rapid overall debinding rate.

In general, a feedstock may include a powder of a material, a primarybinder, and a secondary binder. The powder of the material may include ametal, a metal alloy, or a ceramic intended for a final, fabricatedobject. The primary binder retains a net shape during an initialfabrication process, and is removed during a debinding step. Thesecondary binder retains the shape of a debound object, and may beremoved in a final densification process (e.g., a sintering process).

Useful metals for the powder of the feedstock may, for example, includecopper and copper alloys, tungsten and tungsten alloys, and hard metalssuch as tungsten carbide or other carbides. Hard metals may be usefullycoated with another metal, such as a cobalt or the like, to facilitatemixing and flow in the feedstock. As noted below, diamond or othersuperhard materials may also or instead be used in a similar manner.

Different materials in the feedstock may have different functionalproperties. Thermal properties may be usefully controlled through theuse of specifically alloyed materials. For example, certain materialssuch as tungsten copper, molybdenum copper, aluminum nitride, andcombinations thereof have good heat dissipation and are useful in heatsinks or in other thermal management applications. For these types ofmaterials, where the independent constituents have vastly differentdensities, the two materials may be physically coupled, such as bycoating copper particles with tungsten or molybdenum to obtain moreuniform particles that more readily remain distributed throughout aflowable medium. Similarly, some alloys have low thermal expansion thatmay be usefully employed, e.g., for bimetallic structures that constrainthermal deformation, for forming hermetic seals in thermally variedenvironments, or other applications where low or controlled thermalexpansion is desired. For example, a variety of nickel iron alloys arecommercially available and suitable for fabrication of objects withcontrolled thermal expansion.

Magnetic properties may also or instead be controlled through the use ofmagnetic alloys, typically using elements such as iron, nickel and/orcobalt. For example, useful magnetic alloys suitable for delivery in anFFF context may include FeSi, FeNi, neodymium iron boron, and samariumcobalt.

Mechanical properties of a three-dimensional object formed through FFFmay also or instead be controlled through various strengtheningtechniques. For example, oxide dispersion strengthening or “Zenerpinning” may be used to strengthen sintered materials through theintroduction of oxides that limit grain growth during sintering toresult in a microstructure having greater strength. A variety ofsuitable oxides, such as Al₂O₃ or Y₂O₃, may be combined with otherpre-alloyed powders to produce an oxide dispersion strengthened (ODS)material with greater strength and hardness than a non-ODS counterpart.More generally, nano-dispersions of oxides, carbides, nitrides orborides may be used to strengthen the resulting material. Othertechniques may also or instead be used to strengthen a MIM-basedmaterial. For example, a feedstock containing carbon nanotubes can beextruded and sintered while the carbon nanotubes remain intact, thusproviding a useful strengthening agent for FFF parts. In another aspect,materials may be hardened with diamonds or the like using, e.g., diamondpowder coated with a metal such as nickel, cobalt, or copper. Thecoating of soft metal helps to prevent segregation prior to sinteringand creates a more uniform distribution of two different phases (harddiamond and soft metallic).

Any of the foregoing may be disposed in a composition containing aprimary and secondary binder suitable for extrusion in a FFF process,either alone or in combination with other alloys or additives accordingto desired attributes of the final, fabricated object. In one aspect, avariety of feedstock types may be provided (where the feedstocks havemutually compatible binder systems, e.g., suited for a common debind andsinter mechanism), and an object may be fabricated from a computer modelthat specifies different characteristics in different locations, wherethe appropriate material is deposited in the appropriate locationaccording to the computer model. Thus, for example, features such asmagnetism, density, electrical conductivity, thermal expansion, thermalconductivity, and strength may be deployed at controlled locationswithin an object according to a user-provided model.

In certain instances, the feedstocks extruded to form three-dimensionalobjects according to one or more of the methods described herein may besubjected to significant forces at various stages of the process, withstorage, handling, and fabrication presenting particular risk forinadvertent application of destructive forces to a feedstock. As anexample, feeding a feedstock into a three-dimensional printer caninclude gripping the feedstock (e.g., using one or more of the drivewheels 702, 704 in FIG. 7). However, in instances in which the bindersystem of the feedstock is soft or brittle, the application of a largegripping force to a feedstock may deform or break the feedstock and,conversely, the application of a low gripping force may be insufficientto move the feedstock through a nozzle. Thus, as described in greaterdetail below, a feedstock may advantageously include a jacket disposedabout a core to reduce the likelihood of damage to the feedstock priorto or during extrusion while nevertheless facilitating the use of powdermaterial and/or binder systems desirable for formation of athree-dimensional object.

Referring now to FIGS. 8A-C, a feedstock 800 may include a core 802 anda jacket 804 about the core 802. The jacket 804 may have a hardnessgreater than a hardness of the core 802 at an extrusion temperature ofthe feedstock 800. As used herein, the term “hardness” should beunderstood to include resistance to shape change (e.g., a permanentshape change) under application of a substantially compressive force.Thus, for example, hardness of the jacket 804 relative to hardness ofthe core 802 may be expressed as differences on any one or more ofvarious different scales of hardness known in the art. As a specificexample, the jacket 804 may have a Shore hardness greater than a Shorehardness of the core 802, with the Shore hardness of each materialmeasured on the same scale (e.g., the Shore A scale or the Shore Dscale).

The use of the Shore hardness as a measurement of mechanical performanceof the feedstocks is intended to be illustrative of a more general setof mechanical properties of materials representing various, differentaspects of the deformation of a material. For example, the Shorehardnesses are proportional to the force needed to deform a materialwith an indenter, and are thus a measurement of the amount of force agripping mechanism can apply to a material before the material fails.Other important metrics may, further or instead, include tensileelongations of materials of the core 802 and the jacket 804, which willgenerally quantify the ability of such materials to tolerate thedeformation induced by gripping mechanisms without catastrophic failure.Additionally, or alternatively, other measurements may be used toquantify the relative mechanical performance of the core 802 and thejacket 804. Other useful metrics may include Rockwell hardnesses, thearea under the curve of a stress-strain measurement for a material, Izodimpact energies, and Charpy impact energies. In general, the jacket 804may have a quantifiably higher mechanical performance (e.g., as measuredaccording to one or more of the parameters described herein) than thecore 802.

In general, the core 802 and the jacket 804 may advantageously decouplecertain physical characteristics of the feedstock 800 related to properextrusion of the feedstock 800 from certain physicochemicalcharacteristics required in a three-dimensional object formed from theextrusion of the feedstock 800. As an example, the core 802 may includea binder system and a powder material suspended in the binder system, asmay be generally useful for imparting certain physicochemical propertiesto a three-dimensional object such that the three-dimensional object maybe processable into a dense, final part. With the powder suspended inthe binder system, however, the core 802 may be brittle or otherwisesusceptible to unintended damage by forces required to extrude thefeedstock 800 through a nozzle, such as any one or more of the nozzlesdescribed herein. Accordingly, the jacket 804 may include a secondpolymer useful for imparting the feedstock 800 with overall physicalproperties such that the feedstock 800 may be sufficiently robust towithstand forces associated with transport, handling, storage,extrusion, or combinations thereof. As a specific example of a usefulphysical property provided by the jacket 804, at a temperature of abouttwenty-three degrees Celsius, the feedstock 800 may be spoolable withoutfracture on a spool with a diameter of at most about thirty-six inchesand at least a diameter greater than a diameter of the feedstock—aphysical characteristic useful for storing and transporting thefeedstock 800 and, further or instead, for continuously feeding thefeedstock 800 during a fabrication process. As an additional oralternative specific example of useful physical property provided by thejacket 804, at a temperature of about twenty-three degrees Celsius, thefeedstock may be substantially rigid—a physical characteristic useful,for example, for facilitating handling of the feedstock 800.

The core 802 may include a powder material, such as any one or more ofthe powder materials described herein. Thus, for example, the powdermaterial may include a sinterable or otherwise thermally processablepowder. The powder material may have a concentration in the core 802such that shrinkage of a three-dimensional part formed from thefeedstock 800 is acceptable (e.g., to within specified designtolerances). Thus, as a more specific example, the powder material canhave a concentration in the core within ±10 volume percent of a tapdensity of the powder material. As used herein, the tap density ofparticles is the bulk density of a powder of the particles after acompaction process specified in ASTM B527, entitled “Standard TestMethod for Tap Density of Metal Powders and Compounds,” the entirety ofwhich is incorporated herein by reference.

The binder system in the core 802 may include a primary binder and asecondary binder. The primary binder and the secondary binder may be anyone or more of the respective primary binders and secondary bindersdescribed herein, unless otherwise specified or made clear from thecontext. Thus, as an example, the primary binder may retain a net shapeof the powder material during a primary debind process (e.g., catalyticdebind process) applied to a three-dimensional object formed fromextrusion of the feedstock 800. Further, or instead, the secondarybinder may retain a net shape of the powder material during a secondarydebind process, which may include a thermal sintering cycle. As aspecific example, the secondary binder may include polypropylene,polyethylene, poly(methyl methacrylate) or another high molecular weightpolymer.

At least one of the primary binder and the secondary binder of thebinder system in the core 802 may include a first polymer. The firstpolymer may be any one or more of the polymers described herein as beinguseful for a primary binder and/or a secondary binder, as the case maybe. That is, the first polymer may be useful for imparting certainphysicochemical properties to a three-dimensional object formed fromextrusion of the feedstock 800 and, optionally, through one or morestages of processing as the three-dimensional object is densified into afinal part. As an example, therefore, the first polymer may be polymer(e.g., polystyrene) useful for providing sufficient strength to athree-dimensional object formed from extrusion of the feedstock 800.

The jacket 804 may include a second polymer. The second polymer in thejacket 804 may, in some instances, complement one or more physicalproperties of the first polymer in the core 802. That is, while thefirst polymer may be selected for certain physicochemical propertiesimparted by the first polymer to a three-dimensional object formed fromextrusion of the feedstock 800, the second polymer may be selected toachieve certain physical properties in the feedstock 800 prior toextrusion, or to enhance the performance of the extrusion process.

In certain instances, the second polymer may be selected to impartstrength to the feedstock 800 such that the feedstock 800 may bettersuited to withstand forces and/or temperatures that may be encounteredduring transportation, handling, and extrusion of the feedstock 800. Asan example, the second polymer may have a molecular weight greater thana molecular weight of the first polymer (or, in instances in which thebinder system includes two or more polymers, greater than an average ofmolecular weights of two or more polymers). As a specific example, thesecond polymer may be a high molecular weight polymer (e.g., polystyreneor polypropylene). With a higher molecular weight, the second polymer ofthe jacket 804 may have a higher melt temperature than the first polymerof the core 802. Further or instead, the second polymer of the jacket804 may have a polymer chain longer than a polymer chain of the firstpolymer of the core 802. Additionally, or alternatively, the secondpolymer may have a Shore D hardness greater than a Shore D hardness ofthe first polymer at the extrusion temperature for the feedstock 800.

In certain implementations, one or more components of the feedstock 800may be distributed in both the core 802 and the jacket 804, as may beuseful for reducing sharp transitions in material properties. Thus, insome instances, the jacket 804 may contain an amount of the powdermaterial. For example, a volumetric percentage of the powder material inthe jacket 804 may be less than a volumetric percentage of the powdermaterial in the core 802. Additionally, or alternatively, the bindersystem may include the second polymer. That is, properties of the secondpolymer that make it useful as part of the jacket 804 may be useful asat least a portion of the secondary binder used to support a net shapeof a three-dimensional object through densification. In general,however, the volumetric percentage of the second polymer in the jacket804 may be greater than a volumetric percentage of the second polymer inthe core 802.

FIG. 9 is a flow chart of an exemplary method 900 of forming a compositefeedstock. In particular, unless otherwise specified or made clear fromthe context, it should be appreciated that the exemplary method 900 maybe used to form the feedstock 800 (FIG. 8) for extrusion by any one ormore of the systems described herein and according to any one or more ofthe methods described herein.

As shown in step 902, the exemplary method 900 may include extruding acontinuous core including a binder system and a powder material. Thepower material may include a powder of any one or more of the materialsdescribed herein and, more specifically, may include a powder of ametal, a metal alloy, a ceramic or combinations thereof. Further, orinstead, the powder may include a sinterable powder. As may be usefulfor limiting shrinkage of a three-dimensional part during densificationinto a dense, final part, the powder may have a concentration in thecontinuous core within ±10 volume percent of a tap density of the powdermaterial. The binder system, likewise, may include any one or more ofthe binder systems described herein, unless otherwise specified or madeclear from the context. Accordingly, it should be understood that thebinder system may include a primary binder and a secondary binder, theprimary binder suitable for retaining a net shape of the powder materialduring a primary debind process, the secondary binder suitable forretaining a net shape of the powder material during a thermal sinteringcycle, and at least one of the primary binder and the secondary binderincluding a first polymer. The primary debind process may include anyone or more of chemical debinding, supercritical debinding, catalyticdebinding, thermal debinding, and wick debinding.

As shown in step 904, the exemplary method 900 may include forming ajacket of a jacket material about the continuous core. For example,forming the jacket may include coextruding the jacket material aroundthe continuous core. Further, or instead, forming the jacket may includespraying the jacket material onto the continuous core or dipping thecontinuous core in a liquid form of the jacket material. At apredetermined temperature (e.g., about twenty-three degrees Celsius),the jacket material may have a Shore hardness greater than a Shorehardness of the continuous core. In this way, therefore, the jacket canprotect the continuous core from forces that, in the absence of thejacket, would be likely to damage the continuous core or otherwiseinterrupt extrusion of the core to form a three-dimensional object.

In certain instances, the binder in the core may include a low molecularweight polymer, and the jacket may include a crosslinker for the lowmolecular weight polymer (e.g., a polymer with a molecular weight of nogreater than 100,000 g/mol) that can initiate crosslinking of the lowmolecular weight polymer to provide a greater strength and/or effectivemolecular weight in an extruded material. Cross-linking may include anycreation of ionic or covalent bonds among polymer chains, which may beused, e.g., to increase hardness and melting point of polymericmolecules. In general, cross-links can be formed by chemical reactionsinitiated, e.g., by heat, pressure, change in pH, electromagnetic energyand so forth. For example, crosslinking to achieve a furtherpolymerization of the low molecular weight polymer may be triggerableduring extrusion by an application of heat, light, mechanical energy orthe like, which may, e.g., activate the crosslinker in the jacket orinitiate mixing or the like between the jacket and the core. Forexample, the crosslinking may be triggered by an application of heat atan extrusion temperature for the feedstock, e.g., at least one hundreddegrees Celsius or some other suitable temperature. In another aspect,the crosslinker may include a liquid crosslinker or the like that isencapsulated within the jacket in a material that can be disrupted orotherwise stimulated to release the crosslinker, e.g., with theapplication of ultrasound energy as the feedstock is extruded. Theappropriate polymer, crosslinker and crosslinking conditions will behighly system dependent. A variety of suitable crosslinking techniquessuch as polymerization of a partially polymerized resin with acrosslinking reagent are known in the art, and may be adapted for usewith a core of polymeric binder material and a jacket containing acrosslinker as contemplated herein.

Conventional MIM feedstock is relatively brittle. Thus, even where suchmaterials are suitable for use with FFF-type equipment, the brittlenature of conventional MIM feedstock is not well suitable for storing,handling, or dispensing non-linear segments of MIM filament tofacilitate continuous fabrication. More specifically, even where abinder system or matrix of a conventional MIM material is capable ofsubstantial deformation to accommodate coiling, spooling or the like, acomposite of the matrix that is loaded with metal powder or the likewill reach a local elastic limit much sooner than the unloaded bindermatrix. To address this challenge, the binder system may include apolymer with a high elastic limit such as an elastomer. This may, forexample, include a thermoplastic elastomer such as a thermoplasticpolyurethane (TPU), polyamide-polyether copolymers, and other similarpolymers. These polymers may be unsuited for use in a FFF processbecause they are soft, and tend to buckle under loads in a manner thatinterferes with driving through an extrusion system. However, by loadingthese otherwise unsuitable polymers with a powder metallurgy material orthe like, the stiffness of the composite can be improved to permit usein extrusion generally, and FFF processes in particular. Thus, althoughthermoplastic elastomers are not used in conventional MIM feedstock, andalthough thermoplastic elastomers are not well-suited to a FFFprocesses, these two categories of materials can be advantageouslycombined to yield a flexible feedstock suitable for coiling, and furthersuitable for extrusion in a FFF process to fabricate a green part fordebinding and sintering into a metal object. This may be adapted for usewith a wide range of materials including the various alloys describedherein and any other metal alloy or the like suitable for mixture with apolymer for extrusion, and for subsequent debinding and sintering into afinal, net shape object.

Another challenge to spooling MIM filament is that, even where a moreflexible binder system is used, the filament will tend to break at theinterface between the binder system (the polymer) and powdered particles(e.g., particles of a metal alloy), which tend to form a weak bond toone another. A variety of techniques are known in polymer chemistry forcompatibilization of polymers with polymers or other materials to createinteractions that mechanically overcome immiscibility between the twoand provide a better blended combination. Coupling agents similarlyprovide bonding agents between polymers and other materials. In general,any molecule or material with a first moiety having an affinity for thepowder and a second moiety having an affinity for the polymer may beused to enhance the bond between the two as contemplated herein. Onesuch agent that compatiblizes a metallic powder blended into a non-polarbinder system is stearic acid—possessing both non-polar and polarmoieties that bond with the non-polar binder system and the metalsurface, respectively. Similarly, polymer-compatible coatings—or apre-coating of the thermoplastic elastomer from the binder system—may beadded to the powder to facilitate improved mechanical bonding between apowdered loading material (e.g., a metal alloy) and a binder system.Still more generally, any materials and/or techniques that promotemechanical coupling between an otherwise immiscible polymer and metalpowder may be used to yield a more flexible composite with greaterstrength under flexure—particularly resistance to fracture at theinterface between materials—that is suitable for spooling and use in aFFF process as contemplated herein.

According to the foregoing, in one aspect there is disclosed herein abuild material for additive manufacturing, e.g., using fused filamentfabrication, comprising a binder system that contains a first polymersuch as a thermoplastic elastomer, the binder system loaded greater than50% by volume with a powder formed of a metal or metal alloy. The buildmaterial may further include a bonding agent to improve a mechanicalbond between the binder system and the powder.

The binder system may include a second polymer forming a primary binderfor the build material that can be removed from the build materialusing, e.g., chemical debinding, supercritical debinding, wickdebinding, catalytic debinding, or thermal debinding. In another aspect,the thermoplastic may be the primary binder, or the thermoplasticelastomer may include a thermoplastic elastomer alloy with componentsthat can be selectively removed by debinding as generally contemplatedherein. In another aspect, the polymer may form a secondary binder(e.g., for a brown part) within the binder system, and a primary bindermay be formed of paraffin wax, plastic, oil, or some other conventionalprimary binder material suitable for debinding from the build material.

In general, any combination of polymers, powders and bonding agents maybe used, preferably to yield a filament with diameter of between 1 and 4mm (such as FFF industry standards of 1.75 mm or 3.0 mm) and a minimumbending radius before fracture of no greater than twelve inches, or nogreater than six inches, e.g., for more compact spooling. In anotheraspect, a FFF process may be adapted for use with less coilablematerials by using large-radius spools to accommodate a larger radius ofcurvature for filament feedstock.

In another aspect, the primary or secondary binder may include ahighly-branched polymer. The melt strength of commercially availableliquefied metal injection molding materials is generally too low forfused filament fabrication. Further, the tensile elongations of thesematerials are also low, limiting feeding mechanisms. In the case ofinjection molding of such materials, a high emphasis is placed onlowering viscosities to achieve better flow during the injectionprocess, and the engineering of such materials to achieve high meltstrengths was not a design goal, leading to the use of linear polymersin injection molding applications.

However, it has been determined that the binder system for extruded MIMmaterials may usefully incorporate highly branched polymers that, inproper combination with a powdered metal or similar build material, forma composite with advantageous melt, extrusion and debind properties.Thus, in one aspect, a MIM material with a secondary binder composed inpart of a highly-branched polymer is disclosed. The branched polymericspecies may be branched variants of the polymers common in the art assecondary binders for MIM materials. In one embodiment, if a moderateenhancement of melt strength and ductility is desired, a high-densitypolyethylene secondary binder may be replaced with a linear low-densitypolyethylene secondary binder exhibiting a moderate amount of branching.If a larger enhancement of these properties is desired, an HDPEsecondary binder may be replaced with a low-density polyethylene (LDPE),which exhibits a substantially greater amount of branching. Increases inbranching are generally attended by increases in viscosity. It will bereadily apparent to one skilled in the art that the resulting ductilityand melt strength of the binder may be continuously varied withincreasing branching of the secondary binder via suitable chemicalsynthesis techniques, that any number of branched polymers may beblended with various linear polymers to achieve suitable properties.Further, the use of a branched secondary binder is not limited topolyethylene grades, but may be usefully applied to any other secondarybinder systems, including polypropylene and polymethylmethacrylate.

In another aspect, if the primary binder is of sufficiently highmolecular weight, such that branching will substantially affect themechanical and rheological properties of the MIM material, thehighly-branched species may be the primary binder. Such primary bindersinclude the polyoxymethylene (often called POM or polyacetal) bindersused in catalytic debinding, as well as the high molecular weightprimary binders disclosed herein for obtaining higher melt strengthmaterials that hydrolyze during debinding (e.g. thermoplasticpolysaccharides, polyglycolic acid, andpoly(lactide)-co-(caprolactone)).

The following description contemplates a number of polymer-based bindersystems that can advantageously be employed in a build material for anextrusion-based additive manufacturing process for sinterable, net shapeobjects. In prior art in metal injection molding materials, a primarybinder composed of low molecular weight molecules is typically used asit provides a sufficient amount of green body strength andsimultaneously allows the mold to be filled properly during an injectionmolding process. In that context, the low molecular weight moleculesalso permit the primary binder to be dissolved quickly during primarydebinding. Typical molecular weights used for such applications arebetween several hundred and several thousand g/mol, with few primarybinder components approaching or exceeding ten thousand g/mol inindustrial practice. Typical melt flow rates for such low molecularweight molecules are above around 100 g/10 minutes in ASTM D1238 testingat 200° C. with a 5-kg load. Indeed, many such binder components exhibita melt flow rate substantially higher than this, with melt flow ratesbeing above 400 g/10 min at 190° C. with a 2.16 kg load.

However, in fused filament fabrication and other similar extrusion-basedadditive fabrication processes, the requirements are different. Forexample, a high flow rate may be an impediment to controlled extrusionand/or shape retention of a fabricated object. Thus, for theseprocesses, a reasonably high strength and viscosity permits mechanicalextrusion and advantageously retains shape for consistent, high-qualityresults. Similarly, a reduced thermal expansion coefficient may bedesired to prevent warping, cracking or other thermally induced stressdeformation. While it is possible to obtain these properties by avoidinglow molecular weight polymers in the primary binder, the use of highermolecular weight polymers comes with a complementary disadvantage in theform of slower debind rates. In one aspect, some of the build materialsdescribed herein can resolve these apparently contradictory designconstraints using a moderate-to-high molecular weight component in theprimary binder, even in a small volume or weight fraction, provided thatthe polymer has a corresponding solvent or the like that can maintaindebind rates at a practical level. A number of techniques and polymersystems are described below that use this approach to achieve practical,extrudable, sinterable build materials with a dissolvable or otherwisechemically-removable polymeric primary binder.

The terms “high molecular weight” and “low molecular weight” are usedfrequently in the following description to distinguish between many ofthese polymer systems by generally dividing polymers into those withmolecular weights above and below a value somewhere between ten thousandand one-hundred thousand grams/mol. In general, these are relative termswithout precise delineation. For example, in the context of polymers andsimilar materials, a low molecular weight component (e.g., a polymer)may be a component with a molecular weight of less than about tenthousand grams/mol, a moderate molecular weight component may be acomponent with a molecular weight of between about ten thousandgrams/mol and one-hundred thousand grams/mol, and a high molecularweight component may be a component with a molecular weight greater thanabout one-hundred thousand grams/mol. However, because these terms arerelative, different sources may ascribe different boundaries to thesegroups, and the boundaries may also vary according to particular polymersystems. That is, one polymer may begin to exhibit properties of ahigh-molecular weight component—such as high viscosity, high melttemperature, high hardness and so forth—at a very different molecularweight than another polymer or polymer system. Thus, these terms shouldbe viewed in context to represent, e.g., general ranges rather thanspecific points of division for the properties of polymeric systems. Forexample, the term “high molecular weight” may be used in a relativesense to indicate a greater molecular weight than another polymer orcomponent, or the term “high molecular weight” may be used tocharacterize the properties of a component in terms of flow, hardnessand so forth. For example, in the context of extrudable build materials,a “moderate molecular weight” component may be any component exhibitinga melt flow rate between around ten to one hundred g/10 min. in ASTMD1238 testing at 200° C. with a 5-kg load, and a “high molecular weight”component may be any component with a melt flow rate less than ten g/10min. under similar conditions. Thus, mechanical properties may be a moreuseful guide to distinguishing among different classes of polymers thatare used in the polymeric binder systems contemplated herein. However,the molecular weight can be readily and accurately determined using anumber of well-known techniques, and where molecular weight provides auseful, relative guide to mechanical, rheological, and thermalproperties (e.g., hardness, strength, viscosity, melt temperature) andchemical properties (e.g., dissolvability), molecular weight is usedherein as a proxy for these characteristics of a build material toprovide a modicum of specificity.

FIG. 10 is a flow chart of an exemplary method 1000 of additivemanufacturing using a spoolable feedstock. The feedstock may include abinder system and a powder material dispersed in the binder system. Thebinder system may include a primary binder and secondary binderseparately removable from a three-dimensional object formed from thefeedstock. The primary binder may include an aggregate of low molecularweight polymers in a physically crosslinked relationship to one another,and the physically crosslinked relationship of the aggregate of lowmolecular weight polymers may be reversible through exposure to a debindsolution. In general, reversibility of the physical crosslinking may beadvantageously used to provide different material properties atdifferent stages of an extrusion process. More specifically, asdescribed in greater detail below in the context of the exemplary method1000, the physically crosslinked relationship of the aggregate of lowmolecular weight polymers may be useful for achieving advantageousphysical properties of the feedstock—such as strength and/or flexibilityuseful for moving and handling the feedstock as part of a continuousprocess—while reversing the physically crosslinked relationship in asolvent may facilitate rapid removal of the primary binder during adebinding process applied to a three-dimensional object.

As shown in step 1010, the exemplary method 1000 may include moving oneor more nozzles along an extrusion path relative to a build plate. Forexample, such movement of one or more nozzles can be based on a computermodel according to any one or more of the various different methodsdescribed herein.

As shown in step 1020, the exemplary method 1000 may include extruding afeedstock through the one or more nozzles, with the extrusion of thefeedstock forming a three-dimensional object along the extrusion path.The three-dimensional object may include, for example, a plurality oflayers, each layer coupled to at least one other layer, and each layerincluding the components of the feedstock extruded to form therespective layer. The feedstock may include a binder system and a powdermaterial dispersed in the binder system such that the three-dimensionalobject formed through the extrusion of the feedstock is a green part.For example, the binder system may include a primary binder and asecondary binder separately removable from the three-dimensional objectthrough subsequent processing, as described in greater detail below.While extrusion of a single feedstock is described for the sake ofclarity of explanation, it should be appreciated that a plurality offeedstocks may be extruded as necessary to impart variations in one ormore properties (e.g., physicochemical properties) along thethree-dimensional object.

The binder system may include a primary binder including an aggregate oflow molecular weight polymers in a physically crosslinked relationshipto one another. This physical crosslinked relationship may be useful forimparting strength to the feedstock to facilitate continuously orsubstantially continuously extruding the feedstock. As described ingreater detail below, the physically crosslinked relationship may bereversible through exposure of the primary binder to a solvent.

The primary binder may include a block copolymer which, in general, mayinclude regions arrangeable to form the physically crosslinked structureuseful for imparting strength to the feedstock. As an example, the blockcopolymer may include a first rigid, crystalizable region, a flexibleregion, and a second rigid, crystalizable region. It should beappreciated that the first crystalizable region and the secondcrystalizable region may have the same composition or a differentcomposition. More generally, it should be understood that the blockcopolymer has a structure such that, in the physically crosslinkedrelationship, the rigid, crystalizable regions of a given blockcopolymer are linked with the rigid, crystalizable regions of at leastone other block copolymer. The flexible region of the block copolymermay provide flexibility in the physically crosslinked structure. As anexample, a block copolymer useful in the primary binder may comprise apolystyrene block. For example, a block copolymer may comprise apolystyrene block and a polybutadiene block.

The flexibility imparted to the feedstock by the primary binder mayfacilitate forming the feedstock as a spoolable material. As an example,the feedstock may be a filament for use in a fused filament fabricationprocess and may have a diameter of greater than about 1 mm and less thanabout 4 mm, although larger or smaller diameters are possible. Further,or instead, the filament may have a bending radius at fracture ofgreater than a diameter of the filament and less than about 30 cm, whichcan be useful for arranging the filament in a spool having a sizesuitable for efficient storage, shipping, and handling while providingan amount of material useful in a continuous process. As used herein,the bending radius should be understood to be a radius of a circle aboutwhich the filament may be wrapped. Thus, the bending radius at fractureshould be understood to be the minimum radius of a circle about whichthe filament may be wrapped before the stresses associated with wrappingthe filament about the circle cause the filament to fracture.

More generally, extruding the feedstock through the one or more nozzlesmay include unspooling a spool of the feedstock and moving the feedstock(e.g., using a drive train) toward the one or more nozzles. Unspoolingthe feedstock in this way may be performed at a rate substantially equalto an extrusion rate of the feedstock through the one or more nozzlessuch that the feedstock is continuously fed through the one or morenozzles.

The powder material of the feedstock may be any one or more of thepowder materials described herein. For example, the powder material mayinclude at least one of a metal, a metal alloy, or a ceramic. In certaininstances, the powder material may include a plurality of components(e.g., component materials of stainless steel) thermally processable toalloy with one another in the final part. Further, or instead, thepowder material may have a density in the feedstock within ±10 volumepercent of a tap density of the powder material. It should beappreciated that such loading of the powder material may be useful forproducing a finished part having an acceptable amount of shrinkage.

As shown in step 1030, the exemplary method 1000 may include reversing aphysically crosslinked relationship of an aggregate of low molecularweight polymers of a primary binder of the binder system. For example,reversing physical crosslinking of the aggregate of low molecular weightpolymers of the primary binder may include exposing the primary binderto a debind solution. As an example, the debind solution may include oneor more of acetone or trans-dichloroethylene, which may be particularlysuitable for reversing physical crosslinking in a polystyrene and, morespecifically, in polybutadiene-polystyrene block copolymer.

As shown in step 1040, the exemplary method 1000 may include removingthe low molecular weight polymers of the primary binder from thethree-dimensional object. The secondary binder may include any ofvarious different polymers suitable for retaining a net shape of thethree-dimensional object through processing following debinding of theprimary binder. As an example, the secondary binder may include athermoplastic (e.g., a thermoplastic elastomer). Additionally, oralternatively, the secondary binder may include polypropylene,polyethylene, and poly(methyl methacrylate). In general, it should beunderstood that any one or more of various different debinding processesmay be used to remove the secondary binder from the three-dimensionalobject, with the nature of the debinding process being a function of,among other factors, the composition of the secondary binder. Thus, forexample, the material of the secondary binder may be removable from thepowder material using a thermal debinding process. Further, or instead,the secondary binder may be removable from the three-dimensional objectthrough one or more of chemical debinding, supercritical debinding, wickdebinding, catalytic debinding, or thermal debinding.

As shown in step 1050, the exemplary method 1000 may include removing asecondary binder from the binder system.

As shown in step 1060, the exemplary method 1000 may include densifyingthe powder material in the three-dimensional object to form a finalpart. For example, the powder material can be densified as part of asintering process. Further, or instead, with one or both of the primarybinder and the secondary binder debound from the three-dimensionalobject, the three-dimensional object may be a porous structure andliquid metal infiltration into the porous structure may be usefullyapplied to densify the three-dimensional object into a final part.

In general, metal injection molding (MIM) build materials withwax/polymer binder systems can be difficult to handle at elevatedtemperatures due to low strength at melt or working temperatures, e.g.,above the melt or glass transition temperature of one or more componentsof the blend. In a fused filament fabrication (FFF) context inparticular, however, the low melt strength of conventional MIM buildmaterials can create difficulties when fabricating bridges, overhangs,or other structures that rely on physical stability of the print mediumduring deposition. Similarly, a low melt strength can make it difficultto control extrusion due to uncontrolled flow or oozing at the nozzleexit, e.g. during starting and stopping of an extrusion. ConventionalFFF feedstock is formed primarily or exclusively of high molecularweight components that alleviate these issues, unlike MIM feedstock thattypically contains wax or other materials with less favorable workingcharacteristics at elevated temperatures.

For MIM materials, a low molecular weight component is typically used asa primary binder to facilitate dissolution with chemical orsupercritical debinding. By contrast, one known catalytic debindingsystem is based on approximately 90% polyacetal (also referred to aspolyoxymethylene or POM), along with small amounts of polyethylene andslip additives. The primary binder in such feedstock reacts directlywith a gas and decomposes monomer-by-monomer. While the binder in thismaterial may have a higher molecular weight, it comes with significantdisadvantages. Specifically, this binder system requires ahigh-temperature (˜100 degrees Celsius) nitric acid vapor for debindingin a process that produces formaldehyde as one of its outputs.

An improved feedstock provides the advantages of high molecular weightcomponents—specifically a high-strength melt—along with the convenienceof a non-hazardous, rapid, reactive debind via dissociation of thebinder into smaller molecules. In one aspect, thermoplastic saccharidescan be used as a primary binder that is chemically decomposed (e.g.,depolymerized) in an aqueous solution using enzymes catalyzing thedecomposition reaction. Amylases are one such class of catalysts thatcan facilitate the hydrolytic decomposition of polysaccharides. As afurther advantage, this debinding process creates a waste stream ofaqueous monosaccharides that can be safely handled and disposed of in ahome or office environment. Other polymers provide similar advantages,and are suitable for use as a primary binder in a FFF/MIM buildmaterial.

For example, many polyesters can be hydrolyzed in aqueous media,including polylactic acid (PLA) and polyglycolic acid (PLGA), the rateand mechanisms of the hydrolysis being a strong function of pH,temperature, and molecular weight of the polyesters. By way of morespecific example, under appropriate conditions polyglycolic acid can bedecomposed into monomers via hydrolysis in acidic solution. Such ahydrolysis will form a well-defined waste stream of monomers. For PLGA,this may not sufficiently enhance diffusive kinetics and otherapproaches may be required or desired. For example, for PLGA the largermolecular weight components may initially be decomposed into smallermolecular weight components more rapidly by conducting the hydrolyticdecomposition in alkaline solution, where the PLGA is known to decomposevia random ester cleavage. A combination of a pH where oligomers of theprimary binder are soluble, along with fast decomposition kinetics andmechanisms can provide for a rapid debind of otherwise high molecularweight polymers. For PLGA, alkaline solutions dissolve PLGA oligomers,creating favorable dissolution conditions overall. One may similarlyengineer the decompositions of any hydrolyzing polyester or otherpolymer to yield a sufficiently fast debinding rate.

Other polymers may also or instead be used to further enhance propertiesof the build material to provide greater flexibility, e.g., so that afilament of the build material can be spooled or otherwise stored andhandled in non-linear segments. For example, polymers such aspoly(lactide)-co-(caprolactone) provide attractive elastic propertiesand dissolution behavior, and may simultaneously enhance thecoilability, melt strength, and debinding behavior of the media, thusproviding a useful primary binder in a binder system of a MIM/FFF buildmaterial.

In another aspect, the primary binder may be composed of a polymer thatis physically cross-linked (as opposed to covalently cross-linked), butwhose physical crosslinks dissolve in the presence of a suitablesolvent, thereby achieving a high effective molecular weight duringhandling, coiling, and printing, but a lower molecular weight during thedebinding step. One example of this are copolymers containing styreneblocks. The crystalline styrene blocks dissolve in acetone (among othersolvents), effectively undoing the cross-linkings when exposed to asolution. Note that this is an especially effective chemistry, asthermoplastic elastomers with good elastic properties (for coiling,handling) are typically physically crosslinked, many of them viacrystalline styrene domains. Such a primary binder may be quickly andeasily debound using a solvent suitable for both the crystalline domainsand the flexible chains connecting them.

Other general polymer chemistries provide useful pathways to a mediathat is suitable for FFF processes (sufficient elasticity for spooling,high melt strength). For example, polyethylene glycol (PEG) is an esterthat can hydrolyze via:

R—O—R′+H₂O→R—CH₂—OH+HO—CH₂—R′

This mechanism provides a useful pathway for accelerating debinding ofPEG-PMMA (where PMMA is poly(methyl methacrylate), also known asacrylic) binders to achieve a primary binder with high melt strength andrapid, safe debind.

Similarly, urethane esters can be hydrolyzed according to:

This is another example of a thermoplastic elastomer that can behydrolyzed and solvent debound while exhibiting superior melt strengthand extensional viscosity.

Anhydrides hydrolyze faster than many other polymers, and thus may beparticularly effective for fast debinding in a hydrolysis-baseddebinding process. Polyanhydrides are regularly used in a medicalcontext to degrade in-vivo because the reaction products are generallybiocompatible and non-toxic. These polymers are similarly suitable fordebinding in a home or office context. A useful primary binder systemmay be engineered from a copolymer containing anhydride groupsinterspersed with a second species to tailor thethermoplastic/rheological properties of the polymer as well as itsdecomposition and dissolution kinetics.

Polyamides degrade in the presence of acids (e.g. nylon, etc.). Ingeneral, a polyamide-polyester copolymer may be used as a thermoplasticelastomer that is hydrolytically solvent-debindable. More generally, therates of hydrolysis for various polymers are (from fastest to slowest):anhydride>ester>amide>ether. This hierarchy may be used to selectrapidly hydrolysable binders for use in a polymer binder system ascontemplated herein.

Thus, there is generally disclosed herein a powder metallurgical buildmaterial for use in a fused filament fabrication system, the materialincluding a powdered metal composition, a secondary binder for retaininga shape of the material during a sintering process, and a primarybinder, the primary binder including a high molecular weight polymerselected for chemical debinding with non-hazardous materials.

The high molecular weight polymer may include a polymer that isphysically cross-linked to achieve high effective molecular weight. Thephysical cross-links may include crystalline styrene blocks. Thedebinding process may include dissolution of the physical cross-links inacetone.

The primary binder may, for example, include a thermoplastic saccharide,polylactic acid, polyglycolic acid, poly(lactide)-co-(caprolactone),copolymers containing styrene blocks, polyethylene glycol, PEG-PMMA, aurethane ester, a polyanhydride, or a copolymer of any of the aboveconstituents.

The reactive debinding may include chemical decomposition in an aqueoussolution or hydrolyzation in an aqueous solution. The reactive debindingmay include decomposition into monomers in an acidic solution. Thereactive debinding may include decomposition in an alkaline solution.The reactive debinding may include dissolving physical cross links witha solvent.

The reactive debinding may produce a waste stream consisting of aqueousmonosaccharides.

FIG. 11 is a flow chart of an exemplary method 1100 of additivemanufacturing with a feedstock including a chemically decomposable highmolecular weight polymer as a component of a primary binder of a bindersystem. In general, unless otherwise specified or made clear from thecontext, the exemplary method 1100 may be carried out using any one ormore of the feedstocks described above, with the feedstock including achemically decomposable high molecular weight polymer as a component ofa primary binder system.

As shown in step 1110, the exemplary method 1100 may include moving oneor more nozzles along an extrusion path relative to a build plate. Theone or more nozzles can be moved along the extrusion path relative tothe build plate according to any one or more of the techniques describedherein and, thus, may include computer-controlled movement of the one ormore nozzles, the build plate, or a combination thereof. Further orinstead, such movement may be carried out using any one or more of thedevices and systems described herein.

As shown in step 1120, the exemplary method 1100 may include extruding afeedstock through the one or more nozzles. The feedstock may include abinder system and a powder material dispersed in the binder system, asdescribed in greater detail below. Unless otherwise specified or madeclear from the context, it should be appreciated that the powdermaterial can be any one or more of the powder materials described hereinand, more generally, can be any powder material usefully formable into adense, final part.

The extrusion of the feedstock may form a three-dimensional object alongthe extrusion path. It should be appreciated, therefore, that thethree-dimensional object formed by extrusion of the feedstock may becollectively formed by a plurality of extruded layers (e.g., with eachlayer coupled to at least one other layer). Further, because each layeris formed through extrusion of the feedstock, it should be appreciatedthat each layer includes a powder material, a primary binder of thebinder system, and a secondary binder of the binder system. As describedin greater detail below, at least one component of the primary bindermay be chemically decomposable in the presence of a solvent in which thesecondary binder is less soluble than the primary binder such that theprimary binder and the secondary binder may be separately removable fromthe three-dimensional object as the three-dimensional object isprocessed to form a final part. It is noted that the solvent may be thereactant through which the chemical decomposition takes place, or maycontain other reactants that take part in the decomposition reaction,and may generally contain catalysts to adjust the decompositionkinetics.

As shown in step 1130, the exemplary method 1100 may include exposingthe three-dimensional object to a chemical solution (e.g., a solvent).In particular, the primary binder may include a moderate-to-highmolecular weight polymer chemically decomposable in the solvent duringdissolution of at least a portion of the primary binder from thethree-dimensional object and, thus, removable from the three-dimensionalobject in a waste stream (e.g., a waste stream including aqueousmonosaccharides). As used herein, a high molecular weight polymer shouldbe understood to be a polymer having a molecular weight of greater thanabout 100,000 g/mol and, correspondingly, a low molecular weight polymershould be understood to be a polymer having a molecular weight greaterthan 10,000 g/mol and less than 100,000 g/mol, with waxes and oligomershaving molecular weights less than 10,000 g/mol.

The moderate-to-high molecular weight polymer may include any one ormore of the high molecular weight binders described herein as beingchemically decomposable in a solvent and, in particular, in anon-hazardous solvent. Accordingly, the high molecular weight polymermay include a physically cross-linked polymer (e.g., a polymer includingphysically cross-linked crystalline styrene blocks). Further, orinstead, the high molecular weight polymer of the primary binder mayinclude at least one of a thermoplastic saccharide, polylactic acid,polyglycolic acid, poly(lactide)-co-(caprolactone), copolymerscontaining styrene blocks, polyethylene glycol, PEG-PMMA, a urethaneester, and a polyanhydride. Further, or instead, the high molecularweight polymer may be chemically decomposable in one or more of anaqueous solution or an alkaline solution. In certain implementations,the chemical solution may be an aqueous solution and the high molecularweight polymer may be hydrolysable in an aqueous solution. In someimplementations, the high molecular weight polymer may be chemicallydecomposable (e.g., into monomers) in an acidic solution.

In general, as compared to low molecular weight polymers, waxes, and/oroligomers, the moderate-to-high molecular weight polymer of the primarybinder should be understood to impart certain desirable characteristicsto the primary binder to facilitate better print quality. For example,as compared to low molecular weight polymers and as described above, thehigh molecular weight polymer may have a higher melt strength useful forimproving print quality. However, without chemical decomposition, thedebind rate of the high molecular weight polymer may be long.Accordingly, chemical decomposition of the high molecular weight polymermay be useful for achieving shorter debind times and, thus, fasterfabrication.

In the solvent, the secondary binder may be less soluble than the highmolecular weight polymer and, in certain instances, the secondary bindermay be substantially insoluble in the solvent. As used herein,substantial insolubility of the secondary binder in the solvent shall beunderstood to include total insolubility as well as low amounts ofsolubility (e.g., less than about 5 percent by mass of the secondarybinder dissolving in the solvent as the three-dimensional object isexposed to the solvent). With the difference in solubility of the highmolecular weight polymer and the secondary binder in the solvent, itshould be understood that the secondary binder may support a shape ofthe three-dimensional object as the high molecular weight polymer ischemically decomposed, during a chemical dissolution of at least aportion of the primary binder, for removal from the three-dimensionalobject.

In certain instances, the primary binder may further include a waxsoluble in the solvent as the three-dimensional object is exposed to thesolvent. Such wax may be useful for imparting a desirable viscosity tothe binder system to facilitate extrusion of the feedstock. It should bemore generally understood that the primary binder may additionally oralternatively include any one or more additives useful for imparting adesired physicochemical property to the feedstock.

As shown in step 1140, the exemplary method 1100 may include debindingthe secondary binder from the three-dimensional object. The secondarybindery may include a second polymer, the second polymer having amolecular weight less than or about equal to a molecular weight of thehigh molecular weight polymer such that the second polymer may providesupport structural support to the three-dimensional object as thethree-dimensional object is processed to form a dense, final part. Ingeneral, the secondary binder may be debound from the three-dimensionalobject through any one or more of various different debinding processes(e.g., any one or more of chemical debinding, supercritical debinding,wick debinding, catalytic debinding, or thermal debinding).

As shown in step 1150, the exemplary method 1100 may include densifyingthe powder material in the three-dimensional object to form a finalpart. Densification of the powder material may include sintering and/orinfiltration of the three-dimensional object with a liquid metal.

FIG. 12 is a flow chart of an exemplary method 1200 of additivemanufacturing with a feedstock including a powder material (e.g., anyone or more of the powder materials described herein and in anyconcentration described herein) dispersed in a primary binder and asecondary binder, with the primary binder including a dissolvable highmolecular weight polymer as a component of a primary binder of a bindersystem. The primary binder may include a first high molecular weightpolymer, secondary binder may include a second high molecular weightpolymer, and the first high molecular weight polymer may bepreferentially dissolvable in a solvent to selectively remove the firsthigh molecular weight polymer in a primary debind step applied to athree-dimensional object. Thus, the first high molecular weight polymermay provide structural support to a three-dimensional object while thedissolving of the high molecular weight polymer facilitates rapidlydebinding the primary binder from the three-dimensional object.

The first high molecular weight polymer suitable for use with theexemplary method 1200 may be any of various different high molecularweight polymers dissolvable in a solvent, such as a non-hazardoussolvent, and suitable for extrusion and providing structural support toa three-dimensional object formed by the extrusion. As an example, thefirst high molecular weight polymer may include polystyrene. Further, orinstead, the first high molecular weight polymer may include one or moreof poly(vinyl alcohol) or polyethylene glycol. As an additional oralternative example, the first high molecular weight polymer may includepoly methyl methacrylate.

The second high molecular weight polymer suitable for use with theexemplary method 1200 may be any polymer that has a solubility in thesolvent that is less than a solubility of the first high molecularweight polymer in the solvent. In certain implementations, the secondhigh molecular weight polymer may include one or more of poly(vinylbutyral), polypropylene, polyethylene, or poly(methyl methacrylate).

In general, the first high molecular weight polymer and the second highmolecular weight polymer may each have a respective melt temperaturegreater than about 60 degrees Celsius. Such melt temperatures aregenerally above melt temperatures of wax or other additives that may beincluded in the binder system. Thus, for example, such melt temperaturesmay be useful for reducing the likelihood of deformation or othersimilar damage to the feedstock under extreme conditions associated withstorage, transportation, or handling.

In certain implementations, the binder system may include the first highmolecular weight polymer in a weight percentage of about 30 percent toabout 70 percent. Such percentage of the first high molecular weightpolymer in the binder system may be useful for achieving a balancebetween competing considerations associated with providing suitablesupport to the three-dimensional object while achieving suitableviscosity of the feedstock being extruded. Further, or instead, thebinder system may include at least one additive suitable for achievingone or more physicochemical properties in combination with the firsthigh molecular weight polymer and the second high molecular weightpolymer. For example, the at least one additive may be less viscous thaneach of the first high molecular weight polymer and the second highmolecular weight polymer to achieve viscosity suitable for extrusion ofthe feedstock. Such an additive may include a wax and, further orinstead, the wax may have a weight percentage greater than or equal to aweight percentage of the first high molecular weight polymer in thebinder system. It should be appreciated, however, that otherconcentrations of wax in the binder system may be useful for achieving atarget viscosity. Further, or instead, the additive may include a lowmolecular weight polymer. As an additional or alternative example, theadditive may include any one of stearic acid, ethylene-vinyl acetate(EVA), and linoleic acid.

As shown in step 1210, the exemplary method 1200 may include moving oneor more nozzles along an extrusion path relative to a build plate and,as shown in step 1220, the exemplary method 1200 may include extrudingfeedstock through the one or more nozzles. Unless otherwise specified ormade clear from the context, it should be appreciated that the steps1210 and 1220 are analogous to steps 1110 and 11120 described above withrespect to FIG. 11.

As shown in step 1230, the exemplary method 1200 may include exposingthe three-dimensional object to a solvent (e.g., immersing thethree-dimensional object in a bath of the solvent). The solvent maypreferentially dissolve the first high molecular weight polymer relativeto the second high molecular weight polymer such that exposure of thethree-dimensional object to the solvent may effectively debind the firsthigh molecular weight polymer from the three-dimensional object, leavingthe second high molecular weight polymer supporting thethree-dimensional object. For example, the second high molecular weightpolymer may be insoluble in the solvent as the solvent dissolves thefirst high molecular weight polymer.

The solvent may be any solvent suitable for preferentially dissolvingthe first high molecular weight polymer relative to the second highmolecular weight polymer. Thus, depending on the composition of thefirst high molecular weight polymer and the second high molecular weightpolymer, the solvent may include one or more of an aliphatichydrocarbon, ethyl acetate, acetone, methyl ethyl ketone,trans-dichloroethylene, benzene, or toluene. Further, or instead, thesolvent may include water. Still further or instead, the solvent mayinclude any one or more of 1,4 dioxane, ethyl acetate, benzene,dimethylformamide, or cyclohexanone.

As shown in step 1240, the exemplary method 1200 may include debindingthe second high molecular weight polymer from the three-dimensionalobject. For example, exposing the three-dimensional object to thesolvent may form an open pore structure in the three-dimensional object,and debinding the second high molecular weight polymer may includeremoving at least a portion of the second high molecular weight polymerthrough the open pore structure in the three-dimensional object.

As shown in step 1250, the exemplary method 1200 may include densifyingthe powder material in the three-dimensional object to form a finalpart. Unless otherwise specified, or made clear from the context, thestep 1250 should be understood to be the same as the analogous step 1150described above with respect to FIG. 11.

As shown in step 1260, the exemplary method 1200 may optionally includemachining the three-dimensional object prior to the step 1250 ofdensifying the three-dimensional object. That is, the secondary bindermay provide support to the three-dimensional object such that machiningdoes not unintentionally alter a shape of the three-dimensional object.

The spatial distribution of a binder will now be discussed.

While certain challenges associated with extrusion of feedstock foradditive manufacturing of high quality dense parts (e.g., metal and/orceramic parts) while achieving suitable debinding times have beenaddressed in terms of composition of the feedstock, additional oralternative solutions to such challenges are possible. For example,referring now to FIG. 13, a three-dimensional object 1300 is a greenpart including a spatial gradient of a first binder system 1302 relativeto a second binder system 1304. As described in greater detail below,material of the first binder system 1302 may be placed along areasrequiring structural support and/or requiring high print resolutionwhile material of the second binder system 1304 may be placed alongareas requiring less structural support and/or lower print resolution.The second binder system 1304 may have a higher debind rate than thefirst binder system 1302 such that, as compared to a part formed onlyfrom the first binder system 1302, the three-dimensional object 1300 mayhave a faster debind time.

FIG. 14 is a flow chart of an exemplary method 1400 for additivemanufacturing a three-dimensional object having a spatial distributionof at least one component of a first binder system relative to at leastone component of a second binder system. Unless otherwise specified ormade clear from the context, it should be understood that the exemplarymethod 1400 may be carried out to form the three-dimensional object 1300described above with respect to FIG. 13.

As shown in step 1410, the exemplary method 1400 may include moving oneor more nozzles along an extrusion path relative to a build plate.Unless otherwise specified or made clear from the context, it should beappreciated that the step 1410 is analogous to the steps 1110 and 1210described above with respect to FIG. 11 and FIG. 12, respectively,

As shown in step 1420, the exemplary method 1400 may include extruding afirst feedstock and a second feedstock through one or more nozzles. Thefirst feedstock may include a first powder dispersed in a first bindersystem, and the second feedstock may include a second powder dispersedin a second binder system. Extrusion of the first feedstock and thesecond feedstock, along the extrusion path, may form a three-dimensionalobject having a spatial gradient of at least one component of the firstbinder system relative to at least one component of the second bindersystem. More specifically, the three-dimensional object may have aspatial gradient of a first primary binder of the first binder systemrelative to a second primary binder of the second binder system.

The first primary binder may have a first molecular weight, the secondprimary binder may have a second molecular weight different from thefirst molecular weight. For example, the first molecular weight of thefirst primary binder may be great than the second molecular weight ofthe second primary binder. Because higher molecular weight materialshave lower debind rates, it should be understood that the first primarybinder may have a lower debind rate than a debind rate of the secondprimary binder. Further, because higher molecular weight is generallyassociated with higher melt strength, it should be appreciated that thefirst primary binder may provide higher print resolution and/or improvedstructural support as compared to the second primary binder.Accordingly, the spatial gradient of the first primary binder and thesecond primary binder along the three-dimensional object may be usefulfor realizing the respective advantages of each primary binder whilelimiting the respective drawbacks of each primary binder. As a specificexample, the first primary binder may include polystyrene. Further, orinstead, the second primary binder may include one or more ofnaphthalene, olive oil, or paraffin wax.

In general, the spatial gradient of the first primary binder relative tothe second primary binder may include any of various differentnon-homogenous distributions of a volumetric concentration of the firstprimary binder relative a volumetric concentration to the second primarybinder. Thus, as used herein, a spatial gradient shall be understood toinclude gradual variations of the relative volumetric concentration ofthe first primary binder relative to the second primary binder along thethree-dimensional object, step-changes in distribution in aconcentration of the first primary binder relative to a concentration ofthe second primary binder along the three-dimensional object, andcombinations thereof. As an example, a volumetric concentration of thefirst primary binder on an outer portion of the three-dimensional objectmay be greater than a volumetric concentration of the first primarybinder on an inner portion of the three-dimensional object. As a morespecific example, the inner portion of the three-dimensional object maybe substantially free of the first primary binder. Further, or instead,the outer portion of the three-dimensional object may be substantiallyfree of the second primary binder. Other distributions are additionallyor alternatively possible and, more generally, the first primary bindermay be present in a higher concentration along those portions of thethree-dimensional object benefiting from increased print resolutionand/or improved structural support.

The first binder system and the second binder system may each include arespective secondary binder. In certain implementations, the firstbinder system may include a secondary binder having a compositiondiffering from a composition of a secondary binder of the second bindersystem. In some implementations, however, the secondary binder of thefirst binder system may have substantially the same composition as thesecondary binder of the second binder system. In this context,substantially the same composition shall be understood to account forvariations within typical tolerance levels associated with the materialof the secondary binder.

As shown in step 1430, the exemplary method 1400 may include debindingthe first binder system and the second binder system from thethree-dimensional object to form a brown part. Debinding the firstbinder system and the second binder system from the three-dimensionalobject may include, for example, exposing the three-dimensional objectto one or more solvents to remove at least a portion of one or both ofthe first primary binder and the second primary binder from thethree-dimensional object. Combinations of solvents and primary bindersdissolvable in such solvents may include any such combinations describedherein. Further or instead, debinding the first binder system and thesecond binder system from the three-dimensional object may includethermally processing the three-dimensional object to remove at last aportion of each respective secondary binder from the three-dimensionalobject.

In certain implementations, the second primary binder of the secondbinder system may include a readily evaporable material. Examples ofsuch readily evaporable material include one or more of olive oil,naphthalene, or a low melting point paraffin wax (e.g., with a meltingpoint less than about 60 degrees C.). In instances in which the secondprimary binder of the second binder system is readily evaporable,debinding the second binder system from the three-dimensional object mayinclude evaporating the second primary binder from the three-dimensionalobject. In general, such evaporation occurs quickly and, thus, may offeradvantages with respect to the speed with which a high-quality part maybe formed.

As shown in step 1440, the exemplary method 1400 may include densifyingthe first powder and the second powder in the brown part to form a finalpart. Unless otherwise specified or made clear from the context, thestep 1440 of densifying the first powder and the second powder in thebrown part should be understood to be substantially analogous to thestep 1150 and the step 1250 described above with respect to FIGS. 11 and12, respectively. In general, the first powder and the second powder canbe any one or more of the powders described herein and, thus, mayinclude one or more of a metal, a metal alloy, or a ceramic. Further, orinstead, it should be understood that a composition of the first powdermay be substantially the same as the composition of the second powder.As used in this context, substantially the same composition of the firstpowder and the second powder should be understood to be the same towithin typical production tolerances for producing powdered material.

The above systems, devices, methods, processes, and the like may berealized in hardware, software, or any combination of these suitable fora particular application. The hardware may include a general-purposecomputer and/or dedicated computing device. This includes realization inone or more microprocessors, microcontrollers, embeddedmicrocontrollers, programmable digital signal processors or otherprogrammable devices or processing circuitry, along with internal and/orexternal memory. This may also, or instead, include one or moreapplication specific integrated circuits, programmable gate arrays,programmable array logic components, or any other device or devices thatmay be configured to process electronic signals. It will further beappreciated that a realization of the processes or devices describedabove may include computer-executable code created using a structuredprogramming language such as C, an object oriented programming languagesuch as C++, or any other high-level or low-level programming language(including assembly languages, hardware description languages, anddatabase programming languages and technologies) that may be stored,compiled or interpreted to run on one of the above devices, as well asheterogeneous combinations of processors, processor architectures, orcombinations of different hardware and software. In another aspect, themethods may be embodied in systems that perform the steps thereof, andmay be distributed across devices in a number of ways. At the same time,processing may be distributed across devices such as the various systemsdescribed above, or all of the functionality may be integrated into adedicated, standalone device or other hardware. In another aspect, meansfor performing the steps associated with the processes described abovemay include any of the hardware and/or software described above. Allsuch permutations and combinations are intended to fall within the scopeof the present disclosure.

Embodiments disclosed herein may include computer program productscomprising computer-executable code or computer-usable code that, whenexecuting on one or more computing devices, performs any and/or all ofthe steps thereof. The code may be stored in a non-transitory fashion ina computer memory, which may be a memory from which the program executes(such as random-access memory associated with a processor), or a storagedevice such as a disk drive, flash memory or any other optical,electromagnetic, magnetic, infrared or other device or combination ofdevices. In another aspect, any of the systems and methods describedabove may be embodied in any suitable transmission or propagation mediumcarrying computer-executable code and/or any inputs or outputs fromsame.

It will be appreciated that the devices, systems, and methods describedabove are set forth by way of example and not of limitation. Absent anexplicit indication to the contrary, the disclosed steps may bemodified, supplemented, omitted, and/or re-ordered without departingfrom the scope of this disclosure. Numerous variations, additions,omissions, and other modifications will be apparent to one of ordinaryskill in the art. In addition, the order or presentation of method stepsin the description and drawings above is not intended to require thisorder of performing the recited steps unless a particular order isexpressly required or otherwise clear from the context.

The method steps of the implementations described herein are intended toinclude any suitable method of causing such method steps to beperformed, consistent with the patentability of the following claims,unless a different meaning is expressly provided or otherwise clear fromthe context. So, for example performing the step of X includes anysuitable method for causing another party such as a remote user, aremote processing resource (e.g., a server or cloud computer) or amachine to perform the step of X. Similarly, performing steps X, Y and Zmay include any method of directing or controlling any combination ofsuch other individuals or resources to perform steps X, Y and Z toobtain the benefit of such steps. Thus, method steps of theimplementations described herein are intended to include any suitablemethod of causing one or more other parties or entities to perform thesteps, consistent with the patentability of the following claims, unlessa different meaning is expressly provided or otherwise clear from thecontext. Such parties or entities need not be under the direction orcontrol of any other party or entity, and need not be located within aparticular jurisdiction.

It should further be appreciated that the methods above are provided byway of example. Absent an explicit indication to the contrary, thedisclosed steps may be modified, supplemented, omitted, and/orre-ordered without departing from the scope of this disclosure.

It will be appreciated that the methods and systems described above areset forth by way of example and not of limitation. Numerous variations,additions, omissions, and other modifications will be apparent to one ofordinary skill in the art. In addition, the order or presentation ofmethod steps in the description and drawings above is not intended torequire this order of performing the recited steps unless a particularorder is expressly required or otherwise clear from the context. Thus,while particular embodiments have been shown and described, it will beapparent to those skilled in the art that various changes andmodifications in form and details may be made therein without departingfrom the spirit and scope of this disclosure and are intended to form apart of the invention as defined by the following claims, which are tobe interpreted in the broadest sense allowable by law.

What is claimed is:
 1. A method of additive manufacturing, the methodcomprising: moving one or more nozzles along an extrusion path relativeto a build plate; extruding a feedstock through the one or more nozzles,the feedstock including a binder system and a powder material dispersedin the binder system, the extrusion of the feedstock forming athree-dimensional object along the extrusion path; exposing thethree-dimensional object to a chemical solution, the chemical solutionchemically decomposing a polymer of a primary binder of the bindersystem, and the chemical decomposition of the polymer occurs during achemical dissolution of at least a portion of the primary binder fromthe three-dimensional object as a secondary binder of the binder systemsupports a shape of the three-dimensional object; debinding thesecondary binder from the three-dimensional object; and densifying thepowder material in the three-dimensional object to form a final part. 2.The method of claim 1, wherein the secondary binder is substantiallyinsoluble in the chemical solution to which the three-dimensional objectis exposed.
 3. The method of claim 1, wherein the polymer of the primarybinder is a high molecular weight polymer.
 4. The method of claim 3,wherein the high molecular weight polymer of the primary binder has amolecular weight of greater than about 100,000 g/mol.
 5. The method ofclaim 3, wherein the secondary binder includes a second polymer, and thesecond polymer has a molecular weight less than or about equal to amolecular weight of the high molecular weight polymer.
 6. The method ofclaim 1, wherein the powder material includes one or more of a metal, ametal alloy, or a ceramic.
 7. The method of claim 1, wherein the primarybinder further includes a wax soluble in the chemical solution as thethree-dimensional object is exposed to the chemical solution.
 8. Themethod of claim 1, wherein the primary binder is debound from thethree-dimensional object leaving a waste stream including aqueousmonosaccharides.
 9. The method of claim 1, wherein densifying the powderincludes one or more of sintering the three-dimensional object orinfiltrating the three-dimensional object with a liquid metal.
 10. Afeedstock for additive manufacturing, the feedstock comprising: a powdermaterial; a primary binder containing a high molecular weight polymerchemically decomposable and dissoluble upon exposure to a chemicalsolution; and a secondary binder for retaining, during a thermalprocess, a shape of a part formed from the feedstock, the secondarybinder substantially insoluble in the chemical solution with which thehigh molecular weight polymer is depolymerizable.
 11. The feedstock ofclaim 10, wherein the high molecular weight polymer has a molecularweight of greater than about 100,000 g/mol.
 12. The feedstock of claim10, wherein the chemical solution comprises a catalyst to for thechemical decomposition of the high molecular weight polymer.
 13. Thefeedstock of claim 12, wherein the chemical decomposition occurs viadepolymerization.
 14. The feedstock of claim 10, wherein the highmolecular weight polymer of the primary binder includes at least one ofa thermoplastic polysaccharide, polylactic acid, polyglycolic acid,poly(lactide)-co-(caprolactone), copolymers containing styrene blocks,polyethylene glycol, PEG-PMMA, a urethane ester, and a polyanhydride.15. The feedstock of claim 10, wherein the high molecular weight polymeris chemically decomposable in one or more of an aqueous solution or analkaline solution.
 16. The feedstock of claim 10, wherein the chemicalsolution is an aqueous solution and the high molecular weight polymer ishydrolysable in the aqueous solution.
 17. The feedstock of claim 10,wherein the high molecular weight polymer is chemically decomposable inan acidic solution.
 18. A three-dimensional object comprising: aplurality of layers collectively forming the three-dimensional object,each layer coupled to at least one other layer, and each layer includinga powder material, a primary binder containing a high molecular weightpolymer chemically decomposable and dissoluble with a chemical solution,and a secondary binder for retaining, during a thermal process, a shapeof the three-dimensional object, the secondary binder substantiallyinsoluble in the chemical solution with which the high molecular weightpolymer is chemically decomposable.
 19. The three-dimensional object ofclaim 18, wherein the high molecular weight polymer has a molecular withof greater than about 100,000 g/mol.
 20. The three-dimensional object ofclaim 18, wherein the secondary binder includes a second polymer, andthe second polymer has a molecular weight less than about equal to amolecular weight of the high molecular weight polymer.